Insecticidal Aryl Pyrrolidines

ABSTRACT

The present invention provides novel aryl pyrrolidines having an excellent insecticidal action as insecticides. Aryl pyrrolidines represented by the formula (I) and use thereof as insecticide.

The present invention relates to novel aryl pyrrolidines and the usethereof as insecticides.

WO2005/085216 describes that isoxazoline substituted benzamide compoundsare useful as pest control agents.

The inventors were dedicated to studying to develop novel compoundsexhibiting higher effects and a broad spectrum against animal pests,such as insects and acari. As a result, the inventors found novel arylpyrrolidines showing an excellent, i.e. high activity, having a broadspectrum and are harmless to beneficial insects, such as bees, as wellas effective against insect pests. Particularly to such insects whichare resistant to insecticides, such as organophosphorus or carbamateagents.

The compounds according to the invention are represented by formula (I)

-   wherein-   X which may be same or different, represents halogen, haloalkyl,    nitro, alkyl, alkoxy, cyano, haloalkoxy, alkylthio, alkylsulfinyl,    alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl,    hydroxyl, mercapto, amino, alkylcarbonylamino,    haloalkylcarbonylamino, benzoylamino, alkoxy-carbonylamino,    haloalkoxycarbonylamino, alkylsulfonylamino or    haloalkylsulfonylamino;-   Y which may be same or different, represents halogen, haloalkyl,    nitro, alkyl, alkoxy, cyano, haloalkoxy, alkylthio, alkylsulfinyl,    alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl,    hydroxyl, mercapto, amino, alkylcarbonylamino,    haloalkylcarbonylamino, benzoylamino, alkoxy-carbonylamino,    haloalkoxycarbonylamino, alkylsulfonylamino or    haloalkylsulfonylamino;-   R represents alkyl or haloalkyl;-   m represents 0, 1, 2, 3, 4 or 5;-   n represents 1, 2, 3 or 4;-   G is selected from the group consisting of

-   wherein-   R¹ and R² each independently represents hydrogen; optionally    substituted alkyl, alkenyl, alkynyl, cycloalkyl or alkylsulfonyl;    haloalkylsulfonyl or CH₂—R⁷; or when taken together represent C₂₋₆    alkylene;-   R³ and R⁴ each independently represents hydrogen; cyano; optionally    substituted alkyl, alkenyl, alkynyl, cycloalkyl; or when taken    together represent C₂₋₆ alkylene;-   l represents 1, 2 or 3;-   R⁵ represents hydrogen; alkyl; optionally substituted cycloalkyl;    haloalkyl; cyano; alkenyl; alkynyl; alkylcarbonyl or CH₂—R⁷;-   R⁶ represents formyl, cyano, alkylcarbonyl, alkylthiocarbonyl,    haloalkylcarbonyl, haloalkylthiocarbonyl, alkylaminocarbonyl,    alkylaminothiocarbonyl, dialkylaminocarbonyl,    dialkylaminothiocarbonyl, alkoxyaminocarbonyl,    alkoxyaminothiocarbonyl, alkoxycarbonyl, alkoxythiocarbonyl,    thioalkoxycarbonyl, thioalkoxythiocarbonyl, CO—R⁷, CS—R⁷,    alkylsulfonyl or haloalkylsulfonyl; or alternatively-   R⁵ and R⁶ when taken together with the nitrogen to which they are    attached to form a 3-6 membered ring which contains at least one N    atom and, optionally at least another heteroatom selected from S and    O, wherein the ring is optionally substituted with keto or thioketo;-   or the group consisting of the heterocycles G1 to G9:

-   Z which may be same or different, represents halogen, haloalkyl,    nitro, alkyl, alkoxy, cyano, haloalkoxy, alkylsulfonyl,    haloalkylsulfonyl, hydroxyl or mercapto;-   k¹ represents 0, 1, 2, 3 or 4;-   k² represents 0, 1, 2 or 3;-   k³ represents 0, 1 or 2;-   k⁴ represents 0 or 1;-   R⁷ represents phenyl or heterocyclic ring, which are optionally    substituted with at least one substituent selected from halogen and    C₁₋₆ alkyl; and-   A represents C or N.

Among the compounds of formula (I) of the invention, preferred compoundsare compounds of formula (Ia)

wherein X, Y, R, A, G, Y, n and m are as defined above.

Among the compounds of the formula (I) or formula (Ia) of the invention,further preferred compounds are those wherein

-   X which may be same or different, represents halogen, C₁₋₆    haloalkyl, nitro, C₁₋₆ alkyl, C₁₋₆ alkoxy, cyano, C₁₋₆ haloalkoxy,    C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆    haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆ haloalkylsulfonyl,    hydroxyl, mercapto, amino, C₁₋₆ alkylcarbonylamino, C₁₋₆    haloalkylcarbonylamino, benzoylamino, C₁₋₆ alkoxy-carbonylamino,    C₁₋₆ haloalkoxy-carbonylamino, C₁₋₆ alkylsulfonylamino or C₁₋₆    haloalkylsulfonylamino;-   Y which may be same or different, represents halogen, C₁₋₆    haloalkyl, nitro, C₁₋₆ alkyl, C₁₋₆ alkoxy, cyano, C₁₋₆ haloalkoxy,    C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆    haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆ haloalkylsulfonyl,    hydroxyl, mercapto, amino, C₁₋₆ alkylcarbonylamino, C₁₋₆    haloalkylcarbonylamino, benzoylamino, C₁₋₆ alkoxy-carbonylamino,    C₁₋₆ haloalkoxy-carbonylamino, C₁₋₆ alkylsulfonylamino or C₁₋₆    haloalkylsulfonylamino;-   R represents C₁₋₆ alkyl or C₁₋₆ haloalkyl;-   m represents 0, 1, 2, 3, 4 or 5;-   n represents 0, 1, 2, or 4;-   G is selected from the group consisting of

-   or group consisting of the G1 to G9:

-   wherein-   R¹ and R² each independently represents hydrogen; optionally    substituted C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₇ cycloalkyl;    C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl or CH₂—R⁷; or when taken    together represent C₂₋₆ alkylene;-   R³ and R⁴ each independently represents hydrogen, cyano; optionally    substituted C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₇ cycloalkyl;    or C₁₋₆ alkoxycarbonyl; or when taken together represent C₂₋₆    alkylene;-   l represents 1 or 2 or 3;-   R⁵ represents hydrogen; C₁₋₆ alkyl; optionally substituted C₃₋₇    cycloalkyl; C₁₋₆ haloalkyl; cyano; C₂₋₆ alkenyl; C₂₋₆ alkynyl; C₁₋₆    alkylcarbonyl; or CH₂—R⁷;-   R⁶ represents formyl, cyano, C₁₋₆ alkylcarbonyl, C₁₋₆    alkylthiocarbonyl, C₁₋₆ haloalkyl-carbonyl, C₁₋₆    haloalkylthiocarbonyl, C₁₋₆ alkylaminocarbonyl, C₁₋₆    alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8    carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon    atoms, C₁₋₆ alkoxyaminocarbonyl, C₁₋₆ alkoxyaminothiocarbonyl, C₁₋₆    alkoxycarbonyl, C₁₋₆ alkoxythiocarbonyl, C₁₋₆ thioalkoxycarbonyl,    C₁₋₆ thioalkoxythiocarbonyl, CO—R⁷, CS—R⁷, C₁₋₆ alkylsulfonyl or    C₁₋₆ haloalkylsulfonyl; or-   R⁵ and R⁶ when taken together with the nitrogen to which they are    attached to form a 3-6 membered ring which contains at least one N    atom and, optionally at least another heteroatom selected from S and    O, wherein the ring is optionally substituted with keto or thioketo;-   Z which may be same or different, represents halogen, C₁₋₆    haloalkyl, nitro, C₁₋₆ alkyl, C₁₋₆ alkoxy, cyano, C₁₋₆ haloalkoxy,    C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, hydroxyl or mercapto;-   k¹ represents 0, 1, 2, 3 or 4;-   k² represents 0, 1, 2 or 3;-   k³ represents 0 or 1;-   k⁴ represents 0 or 1;-   R⁷ represents phenyl or a heterocyclic ring, which are optionally    substituted with at least one substituent selected from fluorine,    chlorine, bromine, iodine and C₁₋₆ alkyl; and-   A represents C or N.

Further preferred compounds of the formula (I) or formula (Ia) of theinvention are such compounds wherein

-   X which may be same or different, represents halogen, C₁₋₆    haloalkyl, nitro, C₁₋₆ alkyl, C₁₋₆ alkoxy, cyano, C₁₋₆ haloalkoxy,    C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆    haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆ haloalkylsulfonyl,    hydroxyl, mercapto, amino, C₁₋₆ alkylcarbonylamino, C₁₋₆    haloalkylcarbonylamino, benzoylamino, C₁₋₆ alkoxy-carbonylamino,    C₁₋₆ haloalkoxy-carbonylamino, C₁₋₆ alkylsulfonylamino or C₁₋₆    haloalkylsulfonylamino;-   Y which may be same or different, represents halogen, C₁₋₆    haloalkyl, nitro, C₁₋₆ alkyl, C₁₋₆ alkoxy, cyano, C₁₋₆ haloalkoxy,    C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆    haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆ haloalkylsulfonyl,    hydroxyl, mercapto, amino, C₁₋₆ alkylcarbonylamino, C₁₋₆    haloalkylcarbonylamino, benzoylamino, C₁₋₆ alkoxy-carbonylamino,    C₁₋₆ haloalkoxy-carbonylamino, C₁₋₆ alkylsulfonylamino or C₁₋₆    haloalkylsulfonylamino;-   R represents C₁₋₆ alkyl or C₁₋₆ haloalkyl;-   m represents 0, 1, 2 or 3;-   n represents 0, 1, 2 or 3;-   G is selected from the group consisting of

-   or the group consisting of the heterocycles G1 to G9:

-   R¹ and R² each independently represents hydrogen, C₁₋₆ alkyl which    may be substituted, C₂₋₆ alkenyl which may be substituted, C₂₋₆    alkynyl which may be substituted, C₃₋₇ cycloalkyl which may be    substituted, C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl or CH₂—R⁷;    or when taken together represent C₃₋₅ alkylene;-   R³ and R⁴ each independently represents hydrogen, cyano, C₁₋₆ alkyl    which may be substituted, C₂₋₆ alkenyl which may be substituted,    C₂₋₆ alkynyl which may be substituted, C₃₋₇ cycloalkyl which may be    substituted or C₁₋₆ alkoxy-carbonyl; or when taken together    represent C₃₋₅ alkylene;-   l represents 1 or 2;-   R⁵ represents hydrogen, C₁₋₆ alkyl, C₃₋₇ cycloalkyl which may be    substituted, C₁₋₆ haloalkyl, cyano, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₁₋₆    alkyl-carbonyl or CH₂—R⁷;-   R⁶ represents formyl, cyano, C₁₋₆ alkyl-carbonyl, C₁₋₆    alkylthio-carbonyl, C₁₋₆ haloalkyl-carbonyl, C₁₋₆    haloalkylthio-carbonyl, C₁₋₆ alkylamino-carbonyl, C₁₋₆    alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8    carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon    atoms, C₁₋₆ alkoxyamino-carbonyl, C₁₋₆ alkoxyaminothio-carbonyl,    C₁₋₆ alkoxy-carbonyl, C₁₋₆ alkoxythio-carbonyl, C₁₋₆    thioalkoxy-carbonyl, C₁₋₆ thioalkoxythio-carbonyl, CO—R⁷, CS—R⁷,    C₁₋₆ alkylsulfonyl or C₁₋₆ haloalkylsulfonyl; or alternatively-   R⁵ and R⁶ when taken together with the nitrogen to which they are    attached to form a 3-6 membered ring which contains at least one N    atom and, optionally at least another heteroatom selected from S and    O, wherein the ring is optionally substituted with keto or thioketo;-   Z which may be same or different, represents halogen, C₁₋₆    haloalkyl, nitro, C₁₋₆ alkyl, C₁₋₆ alkoxy, cyano, C₁₋₆ haloalkoxy,    C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, hydroxyl or mercapto;-   k¹ represents 0, 1, 2 or 3;-   k² represents 0, 1 or 2;-   k³ represents 0 or 1;-   k⁴ represents 0 or 1;-   R⁷ represents phenyl or a heterocyclic ring, which are optionally    substituted with at least one substituent selected from fluorine,    chlorine, bromine, and C₁₋₆ alkyl; and-   A represents C or N.

Among those compounds of the formula (I) or formula (Ia), particularlypreferable are compounds wherein

-   X which may be same or different, represents halogen, C₁₋₄    haloalkyl, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy, cyano, C₁₋₄ haloalkoxy,    C₁₋₄ alkylthio, C₁₋₄ alkylsulfinyl, C₁₋₄ alkylsulfonyl, C₁₋₄    haloalkylthio, C₁₋₄ haloalkylsulfinyl, C₁₋₄ haloalkylsulfonyl,    hydroxyl, mercapto, amino, C₁₋₄ alkyl-carbonylamino, C₁₋₄    haloalkylcarbonylamino, benzoylamino, C₁₋₄ alkoxycarbonylamino, C₁₋₄    haloalkoxy-carbonylamino, C₁₋₄ alkylsulfonylamino or C₁₋₄    haloalkylsulfonylamino;-   Y which may be same or different, represents halogen, C₁₋₄    haloalkyl, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy, cyano, C₁₋₄ haloalkoxy,    C₁₋₄ alkylthio, C₁₋₄ alkylsulfinyl, C₁₋₄ alkylsulfonyl, C₁₋₄    haloalkylthio, C₁₋₄ haloalkylsulfinyl, C₁₋₄ haloalkylsulfonyl,    hydroxyl, mercapto, amino, C₁₋₄ alkyl-carbonylamino, C₁₋₄    haloalkylcarbonylamino, benzoylamino, C₁₋₄ alkoxy-carbonylamino,    C₁₋₄ haloalkoxy-carbonylamino, C₁₋₄ alkylsulfonylamino or C₁₋₄    haloalkylsulfonylamino;-   R represents C₁₋₄ alkyl or C₁₋₄ haloalkyl;-   m represents 0, 1, 2 or 3;-   n represents 0, 1, 2 or 3;-   G is selected from the group consisting of

-   or the group consisting of the heterocycles G1 to G9:

-   R¹ and R² each independently represents hydrogen, C₁₋₄ alkyl which    may be substituted, C₂₋₄ alkenyl which may be substituted, C₂₋₄    alkynyl which may be substituted, C₃₋₆ cycloalkyl which may be    substituted, C₁₋₄ alkylsulfonyl, C₁₋₄ haloalkylsulfonyl or CH₂—R⁷;    or when taken together represent C₃₋₅ alkylene;-   R³ and R⁴ each independently represents hydrogen, cyano, C₁₋₄ alkyl    which may be substituted, C₂₋₄ alkenyl which may be substituted,    C₂₋₄ alkynyl which may be substituted, C₃₋₆ cycloalkyl which may be    substituted or C₁₋₄ alkoxy-carbonyl; or when taken together    represent C₃₋₅ alkylene;-   l represents 1 or 2;-   R⁵ represents hydrogen, C₁₋₄ alkyl, C₃₋₆ cycloalkyl which may be    substituted, C₁₋₄ haloalkyl, cyano, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₄    alkyl-carbonyl or CH₂—R⁷;-   R⁶ represents formyl, cyano, C₁₋₄ alkyl-carbonyl, C₁₋₄    alkylthio-carbonyl, C₁₋₄ haloalkyl-carbonyl, C₁₋₄    haloalkylthiocarbonyl, C₁₋₄ alkylamino-carbonyl, C₁₋₄    alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8    carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon    atoms, C₁₋₄ alkoxyamino-carbonyl, C₁₋₄ alkoxyaminothio-carbonyl,    C₁₋₄ alkoxy-carbonyl, C₁₋₄ alkoxythio-carbonyl, C₁₋₄    thioalkoxy-carbonyl, C₁₋₄ thioalkoxythio-carbonyl, CO—R⁷, CS—R⁷,    C₁₋₄ alkylsulfonyl or C₁₋₄ haloalkylsulfonyl; or alternatively-   R⁵ and R⁶ when taken together with the nitrogen to which they are    attached to form a 3-6 membered ring which contains at least one N    atom and, optionally at least another heteroatom selected from S and    O, wherein the ring is optionally substituted with keto or thioketo;-   Z which may be same or different, represents halogen, C₁₋₄    haloalkyl, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy, cyano, C₁₋₄ haloalkoxy,    C₁₋₄ alkylsulfonyl, C₁₋₄ haloalkylsulfonyl, hydroxyl or mercapto;-   k¹ represents 0, 1, 2 or 3;-   k² represents 0, 1 or 2;-   k³ represents 0 or 1;-   k¹ represents 0 or 1;-   R⁷ represents phenyl or a heterocyclic ring, which are optionally    substituted with at least one substituent selected from fluorine,    chlorine, bromine, and C₁₋₄ alkyl; and

In an embodiment of the invention the compounds of the formula (I) orformula (Ia) are compounds wherein

-   X which may be same or different, represents chlorine, fluorine,    bromine, trifluormethyl, difluormethyl, fluormethyl, nitro, methyl,    ethyl, propyl, i-propyl, butyl, t-butyl, 2-methyl-propyl, methoxy,    ethoxy, propoxy, i-propoxy, n-butoxy, t-butoxy, 2-methyl-propoxy,    cyano, trifluormethoxy, difluormethyoxy, fluormethyoxy, thiomethyl,    thioethyl, thiopropyl, thio-i-propyl, thiobutyl, thio-t-butyl,    2-methyl-thiopropyl, methylsulfinyl, ethylsulfinyl, propylsulfinyl,    i-propylsulfinyl, butylsulfinyl, t-butylsulfinyl,    2-methyl-propylsulfinyl, methylsulfonyl, ethylsulfonyl,    propylsulfonyl, i-propylsulfonyl, butylsulfonyl, t-butylsulfonyl,    2-methyl-propylsulfonyl, trifluormethylthio, trifluormethylsulfinyl,    trifluormethylsulfonyl, hydroxyl, mercapto, amino,    methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino,    i-propylcarbonylamino, butylcarbonylamino, t-butylcarbonylamino,    2-methyl-propylcarbonylamino, benzoylamino, methoxy-carbonylamino,    ethoxy-carbonylamino, propoxy-carbonylamino,    i-propoxy-carbonylamino, butyloxy-carbonylamino,    t-butyloxy-carbonylamino, 2-methyl-propoxy-carbonylamino,    trifluormethoxycarbonylamino, C₁₋₆ alkylsulfonylamino or C₁₋₄    haloalkylsulfonylamino;-   Y which may be same or different, represents chlorine, fluorine,    bromine, iodine, trifluormethyl, difluormethyl, fluormethyl, nitro,    methyl, ethyl, propyl, i-propyl, butyl, t-butyl, 2-methyl-propyl,    methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, t-butoxy,    2-methyl-propoxy, cyano, trifluormethoxy, difluormethyoxy,    fluormethyoxy, thiomethyl, thioethyl, thiopropyl, thio-i-propyl,    thiobutyl, thio-t-butyl, 2-methyl-thiopropyl, methylsulfinyl,    ethylsulfinyl, propylsulfinyl, i-propylsulfinyl, butylsulfinyl,    t-butylsulfinyl, 2-methyl-propylsulfinyl, methylsulfonyl,    ethylsulfonyl, propylsulfonyl, i-propylsulfonyl, butylsulfonyl,    t-butylsulfonyl, 2-methyl-propylsulfonyl, trifluormethylthio,    trifluormethylsulfinyl, trifluormethylsulfonyl, hydroxyl, mercapto,    amino, trifluormethylcarbonylamino, methylcarbonylamino,    ethylcarbonylamino, propylcarbonylamino, i-propylcarbonylamino,    butylcarbonylamino, t-butylcarbonylamino,    2-methyl-propylcarbonylamino, 2,2,2,-trichlorethylcarbonylamino,    benzoylamino, methoxy-carbonylamino, ethoxy-carbonylamino,    propoxy-carbonylamino, i-propoxy-carbonylamino,    butyloxy-carbonylamino, t-butyloxy-carbonylamino,    2-methyl-propoxy-carbonylamino, trifluormethoxycarbonylamino, C₁₋₄    alkylsulfonylamino or C₁₋₄ haloalkylsulfonylamino;-   R represents methyl, ethyl, propyl, i-propyl, butyl, t-butyl,    2-methyl-propyl or trifluormethyl, difluormethyl, fluormethyl;-   m represents 0, 1, 2 or 3;-   n represents 0, 1, 2 or 3;-   G represents:

-   -   or alternatively represents the following heterocycles of G1-G9:

-   R¹ and R² each independently represents hydrogen, C₁₋₄ alkyl which    may be substituted, C₂₋₄ alkenyl which may be substituted, C₂₋₄    alkynyl which may be substituted, C₃₋₆ cycloalkyl which may be    substituted, C₁₋₄ alkylsulfonyl, C₁₋₄ haloalkylsulfonyl or CH₂—R⁷;    or when taken together represent C₃₋₅ alkylene;-   R³ and R⁴ each independently represents hydrogen, cyano, C₁₋₄ alkyl    which may be substituted, C₂₋₄ alkenyl which may be substituted,    C₂₋₄ alkynyl which may be substituted, C₃₋₆ cycloalkyl which may be    substituted or C₁₋₄ alkoxy-carbonyl; or when taken together    represent C₃₋₅ alkylene;-   l represents 1 or 2;-   R⁵ represents hydrogen, C₁₋₄ alkyl, C₃₋₆ cycloalkyl which may be    substituted, C₁₋₄ haloalkyl, cyano, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₄    alkyl-carbonyl or CH₂—R⁷;-   R⁶ represents formyl, cyano, C₁₋₄ alkyl-carbonyl, C₁₋₄    alkylthio-carbonyl, C₁₋₄ haloalkyl-carbonyl, C₁₋₄    haloalkylthio-carbonyl, C₁₋₄ alkylamino-carbonyl, C₁₋₄    alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 6    carbon atoms, dialkylaminothio-carbonyl having from 2 to 6 carbon    atoms, C₁₋₄ alkoxyamino-carbonyl, C₁₋₄ alkoxyaminothio-carbonyl,    C₁₋₄ alkoxy-carbonyl, C₁₋₄ alkoxythio-carbonyl, C₁₋₄    thioalkoxy-carbonyl, C₁₋₄ thioalkoxythio-carbonyl, CO—R⁷, CS—R⁷,    C₁₋₄ alkylsulfonyl or C₁₋₄ haloalkylsulfonyl; or alternatively-   Z which may be same or different, represents chlorine, bromine or    iodine, trifluormethyl, nitro, methyl, ethyl, propyl, i-propyl,    butyl, t-butyl, 2-methyl-propyl, cyano;-   k³ represents 0 or 1;-   k⁴ represents 0 or 1;-   R⁷ represents phenyl which may be substituted or a heterocyclic ring    selected from the group consisting of pyridyl, pyrolidinyl,    imidazolyl, triazolyl, oxadiazolyl, tetrazolyl, pyrimidinyl, and    triazinyl which may be substituted, wherein the substituent is at    least one selected from chlorine, bromine, iodine and methyl, ethyl,    i-propyl, n-propyl, 2-methyl propyl, n-butyl and t-butyl; and-   A represents C.

The compounds of the formula (I) or formula (Ia) of the presentinvention have asymmetric carbons, and thus encompass optical isomers.

As used herein, “alkyl” refers to linear or branched C₁₋₁₂ alkyl such asmethyl, ethyl, n- or iso-propyl, n-, iso-, sec-, or tert-butyl,n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl and the like, preferably refers to C₁₋₆ alkyl.

As used herein, “haloalkyl” refers to alkyl groups having 1 to 12carbonatoms, preferably 1 to 6 or 1 to 4 carbon atoms in which at leaston hydrogen atom is exchanged by a halogen. Suitable haloalkyls are forexample CH2F, CHF2, CF3, CF2Cl, CFCl2, CF2Br, CF2CF3, CFHCF3, CH2CF3,CFClCF3, CCl2CF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF2Cl, CF2CF2Br, CFHCH3,CFHCH2F, CFHCHF2, CHFCF3, CHFCF2Cl, CHFCF2Br, CH2CF3, CFClCF3, CCl2CF3,CF2CF2CF3, CH2CF2CF3, CF2CH2CF3, CF2CF2CH3, CHFCF2CF3, CF2CHFCF3,CF2CF2CHF2, CF2CF2CH2F, CF2CF2CF2Cl, CF2CF2CF2Br. The haloalkyl moietycan be substituted by at least one suitable substituent.

As used herein, “alkoxy” refers to alkoxy groups having 1 to 12carbonatoms, preferably 1 to 6 or 1 to 4 carbon atoms. Suitable alkoxygroups are for example methoxy, ethoxy, n-propoxy, i-propoxy, n-, iso-,sec- or tert-butoxy, pentyloxy, oder hexyloxy. The alkoxy moiety can besubstituted by at least one suitable substituent.

Each alkyl moiety in each group having alkyl as a part of itsconfiguration may additionally be illustrated by those same as describedfor “alkyl” above.

“Acylamino” represents, for example, alkylcarbonylamino,cyclopropylcarbonylamino and benzoylamino, wherein alkyl moiety may beillustrated by those same as described for “alkyl” above.

“Halogen” and each halogen moiety in each group substituted with halogenrefer to fluorine, chlorine, bromine and iodine, preferably refer tofluorine, chlorine or bromine.

“Cycloalkyl” refers to C₃₋₈-cycloalkyl such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, preferably refers toC₃₋₇ cycloalkyl.

“Alkenyl” refers to C₂₋₅ alkenyl such as vinyl, allyl, 1-propenyl, 1-(or 2- or 3-) butenyl, 1-pentenyl, preferably refers to C₂₋₄ alkenyl.

“Alkynyl” refers to C₂₋₅ alkynyl such as ethynyl, propargyl, 1-propynyl,butane-3-ynyl, pentane-4-ynyl and the like, preferably refers to C₂₋₄alkynyl.

A “heterocyclic group” refers to a 5 or 6-membered heterocyclic groupcontaining at least one hetero atom selected from N, O or S, whereinsaid ring also refers to a condensed heterocyclic group which may bebenzo-condensed.

Heterocyclic groups are for example furyl, thienyl, pyrrolyl,isoxazolyl, pyrazolyl, oxazolyl, oxathiazolyl, imidazolyl, triazolyl,oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrolidinyl,pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl,quinolyl and the like.

The compounds of the formula (I) or formula (Ia) of the invention may beobtained, for example, by the preparation methods (a) to (j) describedbelow.

Preparation method (a) comprises reacting a compound of formula (II)

wherein X, R and m have the same meanings as defined herein, with acompound of formula (III) or formula (III-a)

-   wherein-   Y, A, G and n have the same meanings as defined herein,-   L¹ represents halogen or a C₁-C₄ haloalkylsulfonyloxy group.

In an embodiment of the preparation method (a), the compounds of formula(II) and formula (III) or or formula (III-a) are reacted in the presenceof a base or in the presence of at least one metallic catalyst.

Preparation methods (b) and (c) for the preparation of compoundsaccording to formula (I) or formula (Ia), wherein G stands for a group—CONR¹R²:

Method (b) comprises reacting a compound represented by the formula (IV)or formula (IV-a)

wherein X, Y, R, A, m and n have the same meanings as defined herein, ora compound represented by the formula (V) or formula (V-a)

wherein X, Y, R, A, m and n have the same meanings as defined herein andL² represents chlorine, bromine, C₁₋₄ alkylcarbonyloxy, C₁₋₄alkoxycarbonyloxy or azolyl,with a compound represented by the formula (VI):

wherein R¹ and R² have the same meanings as defined herein, using acondensation agents, if desired, in the presence of base.

Method (c) comprises reacting a compound represented by the formula (Ib)or formula (Ie):

wherein X, Y, R, R¹, A, m and n have the same meanings as definedherein,with a compound represented by the formula:R²-L³ (VII), wherein R² has the same meaning as defined herein and L³represents chlorine, bromine, iodine, C₁₋₄ alkylsulfonyloxy, C₁₋₄haloalkylsulfonyloxy, arylsulfonyloxy or azolyl, if desired, in thepresence of base.

Preparation method (d) for the preparation of compounds according toformula (I) or formula (Ia), wherein G stands for a group —CSNR¹R²:

Method (d) comprises reacting a compound represented by the formula (If)or formula (Id):

wherein X, Y, R, R¹, R², A, m and n have the same meanings as definedherein, with sulfating agents.

Preparation methods (e), (f) and (g) for the preparation of compoundsaccording to formula (I) or formula (Ia), wherein G stands for

Method (e) comprises reacting a compound represented by the formula(VIII) or formula (VIII-b):

wherein X, Y, R, R³, R⁴, A, l, m, n and L³ have the same meanings asdefined herein, with a compound represented by the formula (IX):

wherein R⁵ and R⁶ have the same meanings as defined herein, if desired,in the presence of base.

Method (f) comprises reacting a compound represented by the formula (X)or formula (X-a):

wherein X, Y, R, R³, R⁴, R⁵, A, l, m and n have the meanings as definedherein, with a compound represented by the formula:

R⁶-L⁴  (XI)

wherein R⁶ has the same meanings as defined herein and L⁴ representsfluorine, chlorine, bromine, C₁₋₄ alkyl-carbonyloxy, C₁₋₄alkoxy-carbonyloxy, azolyl, C₁₋₄ alkylsulfonyloxy, C₁₋₄haloalkylsulfonyloxy, arylsulfonyloxy, if desired, in the presence ofbase.

Method (g) comprises reacting a compound represented by the formula (Ic)or formula (Ig):

wherein X, Y, R, R³, R⁴, R⁶, A, l, m and n have the same meanings asdefined herein, with a compound represented by the formula

R⁵-L⁴  (XII),

wherein R⁵ and L⁴ have the same meanings as defined herein, if desired,in the presence of base.

Preparation method (h) for the preparation of compounds according toformula (I) or formula (Ia), wherein G stands for G1, G6 or G8:

Method (h) comprises reacting a compound represented by the formula(XIII) or formula (XIII-a):

wherein X, Y, A, m and n have the same meanings as defined herein, withdialkoxytetrahydrofuran, 1,2-diformylhydrazine or sodium azide andtrialkyl orthoformate.

Preparation method (i) for the preparation of compounds according toformula (I) or formula (Ia), wherein G stands for G2:

Method (i) comprises reacting a compound represented by the formula(XIV) or formula (XIV-a):

wherein X, Y, A, m and n have the same meanings as defined herein, with1,1,3,3-tetra alkoxypropane.

Preparation method (j) for the preparation of compounds according toformula (I) or formula (Ia), wherein G stands for G2, G3, G4, G5, G6, G8or G9:

Method (j) comprises reacting a compound represented by the formula (XV)or formula (XV-a):

wherein X, Y, R, A, m, n and L¹ have the same meanings as definedherein, with the protonated groups named G2, G3, G4, G5, G6, G8 or G9,namely G2-H, G3-H, G4-H, G5-H, G6-H or G8-H.

According to the present invention, aryl pyrrolidines of the aboveformula (I) or formula (Ia) of the invention exhibit a potentinsecticidal action.

Above mentioned preparation method (a), when using, for example,3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine andN-(4-bromo-2-methylbenzyl)acetamide as starting materials, may berepresented by the reaction formula below.

The preparation method (b), when using, for example,4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoicacid and 2-picolylamine as starting materials, may be represented by thereaction formula below.

The preparation method (c), when using, for example,4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitro-N-(pyridine-2-yl-methyl)benzamideand iodomethane as starting materials, may be represented by thereaction formula below.

The preparation method (d), when using, for example,2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-Nyridine-2-yl-methyl)benzamideand Lawesson reagent as starting materials, may be represented by thereaction formula below.

The preparation method (e), when using, for example,1-[4-(bromomethyl)phenyl]-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidineand benzamide as starting materials, may be represented by the reactionformula below.

The preparation method (f), when using, for example,1-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methanamineand acetyl chloride as starting materials, may be represented by thereaction formula below.

The preparation method (g), when using, for example,N-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzyl}acetamideand iodomethane as starting materials, may be represented by thereaction formula below.

The preparation method (h), when using, for example,4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]aniline and2,5-dimethoxytetrahydrofuran as starting materials, may be representedby the reaction formula below.

The preparation method (i), when using, for example,3-(3,5-dichlorophenyl)-1-(4-hydrazinophenyl)-3-(trifluoromethyl)pyrrolidineand 1,1,3,3-tetraethoxypropane as starting materials, may be representedby the reaction formula below.

The preparation method (j), when using, for example,5-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-fluorobenzonitrileand 1H-1,2,4-triazole as starting materials, may be represented by thereaction formula below.

Many of the compounds of the formula (II), which are the startingmaterials in the preparation method (a), are novel compounds and may besynthesized by the method described below. The compound represented bythe formula (XVI):

wherein X, m and R have the same meanings as defined herein is reactedwith, for example,N-benzyl-1-methoxy-N-[(trimethylsilyl)methyl]methanamine in the presenceof catalysts to obtain the compound represented by the formula (XVII)below:

wherein X, m and R have the same meanings as defined herein, which isthen debenzylated to obtain the compound of the formula (II).

Known compounds having formula (XVI) are for example described in “TheJournal of Organic Chemistry, 1991, vol. 56, pp. 7336-7340”; “TheJournal of Organic Chemistry, 1994, vol. 59, pp. 2898-2901”; “Journal ofFluorine Chemistry, 1999, vol. 95, pp. 167-170”; “WO2005/05085216A”.Such compounds may also be synthesized by the methods described in thesepublications.

Representative examples of the compounds of the formula (XVI) include[1-(trifluoromethyl)vinyl]benzene;1-chloro-3-[1-(trifluoromethyl)vinyl]benzene;1-bromo-3-[1-(trifluoromethyl)vinyl]benzene;1-nitro-3-[1-(trifluoromethyl)vinyl]benzene;1-trifluoromethyl-3-[1-(trifluoromethyl)vinyl]benzene;1,3-difluoro-5-[1-(trifluoromethyl)vinyl]benzene;1,3-dichloro-5-[1-(trifluoromethyl)vinyl]benzene;1,3-difluoro-5-[1-(trifluoromethyl)vinyl]benzene;1-fluoro-2-(trifluoromethyl)-4-[1-(trifluoromethyl)vinyl]benzene;1,2,3-trichloro-5-[1-(trifluoromethyl)vinyl]benzene; or1,3-dimethyl-2-nitro-5-[1-(trifluoromethyl)vinyl]benzene.

Instead of N-benzyl-1-methoxy-N-[(trimethylsilyl)methyl]methanamine inthe above reaction,N-benzyl-1-butoxy-N-[(trimethylsilyl)methyl]methanamine orN-(butoxymethyl)-N-[(trimethylsilyl)methyl]cyclohexylamine may be used.These are well known compounds.

The catalysts used in the above reaction may include trifluoroaceticacid, trimethylsilyl trifluoromethansulfonate, iodotrimethylsilane,cesium fluoride and the like.

The above reaction may be performed according to the methods describedin “Chemistry Letters, 1984, 1117-1120” and “Tetrahedron Letters, 1993,34, 3279-3282”, and the deprotection reaction such as debenzylation maybe performed according to the methods described in “Journal of theOrganic Chemistry, 1984, 49, 2081” and “PROTECTIVE GROUPS in ORGANICCHEMISTRY THIRD EDITION, JOHN WILEY & SONS, INC”.

Representative examples of the compounds of the formula (II) in thepreparation method (a) include:3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidine;3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl) pyrrolidine;3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl) pyrrolidine;3-(3,5-dimethyl-4-nitrophenyl)-3-(trifluoromethyl) pyrrolidine.

Many of the compounds of the formula (III) or formula (III-a), which arethe starting materials in the preparation method (a), are knowncompounds, which may be synthesized by the methods well known in organicchemistry.

Representative examples of the compounds of the formula (III) andformula (III-a), respectively, include: N-(4-bromobenzyl)acetamide,N-(4-iodobenzyl)acetamide.

The reaction of the preparation methods (a), (b), (c), (d), (e), (f),(g), (h), (i) and (j) may be performed in a suitable diluent such asaliphatic hydrocarbons (e.g. hexane, cyclohexane, heptane etc.),aliphatic halogenated hydrocarbons (e.g. dichloromethane, chloroform,carbon tetrachloride, dichloroethane), aromatic hydrocarbons (e.g.benzene, toluene, xylene, chlorobenzene etc.), ethers (e.g.diethylether, dibutylether, dimethoxyethane (DME), tetrohydrofuran,dioxane etc.), esters (e.g. ethyl acetate, ethyl propionate etc.),amides (e.g. dimethylformamide (DMF), dimethylacetamide (DMA),N-methylpyrrolidone etc.), nitriles (e.g. acetonitrile, propionitrileetc.), dimethylsulfoxide (DMSO), water or mixed solvents thereof.

The reaction of the preparation methods (a), (b), (c), (d), (e), (f),(g), (h), (i) and (j) may be performed using the following bases such asalkali metal bases (e.g. lithium hydride, sodium hydride, potassiumhydride, butyl lithium, tert-butyl lithium, trimethylsilyl lithium,lithium hexamethyldisilazide, sodium carbonate, potassium carbonate,cesium carbonate, tripotassium phosphate, sodium acetate, potassiumacetate, sodium methoxide, sodium ethoxide, sodium-tert-butoxide andpotassium-tert-butoxide etc.), organic bases (e.g. triethylamine,diisopropylethylamine, tributylamine, N-methylmorpholine,N,N-dimethylaniline, N,N-diethylaniline,4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine,diazabicycloundecene, diazabicyclooctane, imidazole etc.).

The preparation methods (a), (b), (c), (d), (e), (f), (g), (h), (i) and(j) may be performed within in wide temperature range. Generally, it maybe performed at the temperature in the range from about −78° C. to about200° C., preferably from about −10° C. to about 150° C. Said reaction ispreferably performed at normal pressure although it may be performedunder high pressure or reduced pressure. The reaction time is from 0.1to 72 hours, preferably from 0.1 to 24 hours.

The reaction of preparation method (a) may also be performed usingsuitable metal catalysts such as transition metal catalysts like forexample Pd₂(dba)₃, Pd₂(dba)₃CHCl₃ (dba=dibenzylidene acetone), Pd(OAc)₂,CuI, or Cu₂O. If desired, it may be performed using phosphine ligandssuch as 2,2′-bis(diphenylphosphino)-1,1′-binaphtalene (BINAP),4,5-bis(diphenylphosphino)-9,9-dimethylxanthene(Xantphos)tributylphosphine and the like or amine ligands such as8-quinolinol, proline, N,N-dimethylglycine and the like.

In performing the preparation method (a), for example, 1 mole of thecompound of the formula (II) is reacted with 1 to 3 moles of thecompound of the formula ( ) or formula (III-a) in the presence of 1 to 3moles of base and catalytic amount of Pd₂(dba)₃CHCl₃ and Xantphos in adiluent such as toluene to obtain the respective compound of the formula(I) or formula (Ia) of the invention.

The compounds of the formula (IV) or formula (IV-a), which are used inthe preparation method (b), are novel compounds. They can be synthesizedby the methods described below. The compound of formula (II) may bereacted with a compound represented by the formula (XVIII):

wherein Y, A, n and L¹ have the same meanings as defined herein, R⁸represents hydrogen or C₁₋₄ alkyl, to obtain a compound represented bythe formula (XIX) or formula (XIX-a):

wherein X, Y, R, A, m, n and R⁵ have the same meanings as definedherein. When R⁸ represents C₁₋₄ alkyl, the compound of above formula(XIX) or formula (XIX-a) may be hydrolyzed to obtain the compound of theformula (IV) or formula (IV-a).

The compounds of the formula (XVIII) are known and include for example,the following compounds: methyl 4-iodobenzoate; methyl4-bromo-2-methylbenzoate; ethyl 2-fluoro-4-iodobenzoate; methyl2-chloro-4-iodobenzoate; methyl 2-bromo-4-iodobenzoate; methyl4-fluoro-2-nitrobenzoate; and ethyl4-fluoro-2-(trifluoromethyl)benzoate.

The compounds of the formula (V) or formula (V-a), which are thestarting materials in the preparation method (b), are well knowncompounds.

For example, the compound of formula (IV) or formula (IV-a) may beeasily obtained by the method comprising a reaction with a chlorinatingagent such as thionyl chloride, oxalyl chloride or phosphoruspentachloride, or the method comprising a reaction with an organichalide such as pivaloyl chloride, or the method comprising a reactionwith carbonyl diimidazole or sulfonyl imidazole etc.

Representative compounds of the formula (IV) and formula (IV-a),respectively, in the preparation method (b) include:

4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzoicacid;4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoicacid;4-{3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)pyrrolidin-1-yl}-2-nitrobenzoicacid;4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-(trifluoromethyl)benzoicacid and the like.

Representative compounds of the formula (V) and formula (V-a),respectively, include:4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzoylchloride;4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoylchloride;4-{3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)pyrrolidin-1-yl}-2-nitrobenzoylchloride and the like.

The compounds of the formula (VI), which are the starting materials inthe preparation method (b), are well known compounds.

Representative examples include: methylamine; ethylamine,cyclopropylamine, propargylamine, 2,2,2-trifluoroethylamine,2-picolylamine, 3-aminomethyl-6-chloropyridine and the like.

The reaction of the preparation method (b) may be performed using thefollowing condensation agents: 1,3-dicyclohexyl carbodiimide (DCC),1-ethyl-3-(3′-dimethylaminopropyl)-carbodiimide hydrochloride (WSCI),carbonyldiimidazole (CDI), diethyl cyanophosphate (DEPC),2-chloro-1-methylpyridinium iodide (Mukouyama Reagent) and the like.

In performing the preparation method (b), for example, 1 mole of thecompound of the formula (IV) or formula (IV-a) may be reacted with 1 to3 moles of the compound of the formula (VI) using 1 mole to 3 moles of acondensation agent and, if desired, with catalytic amount of an additivesuch as 1-hydroxybenzotriazole in a diluent (e.g. DMF) to obtain thecorresponding compound of the formula (I) or formula (Ia).

The compounds of the formula (Ib) or formula (Ie), which are thestarting materials in the preparation method (c), are encompassed in theformula (I) or formula (Ia) of the present invention obtained bypreparation method (b).

The compounds of the formula (VII), which are the starting materials arewell known compounds and specific examples include iodomethane,iodoethane and the like.

In performing the preparation method (c), for example, 1 mole of thecompound of the formula (Ib) or formula (Ie) may be reacted with 1 to 5moles of the compound of the formula (VII) in the presence of base in adiluent (e.g. THF) to obtain the corresponding compound of the formula(I) or formula (Ia).

The compounds of the formula (If) or formula (Id), which are thestarting materials in the preparation method (d), are encompassed in theformula (I) or formula (Ia) of the present invention obtained by abovepreparation method (b) or (c).

Sulfurizing agents used in the preparation method (d) may includephosphorus pentasulfide, Lawesson reagent and the like.

In performing the preparation method (d), for example, 1 mole of thecompound of the general formula (If) or formula (Id) may be reacted with0.5 to 3 moles of Lawesson reagent in a diluent (e.g. toluene) to obtainthe corresponding compound of the formula (I) or formula (Ia).

The compounds of the formula (VIII) or formula (VIII-b), which are thestarting materials in the preparation method (e), are novel compoundsand may be synthesized by the method below. The compound of aboveformula (XIX) or formula (XIX-a) may be reduced to obtain the compoundrepresented by the formula (XX) or formula (XX-a):

wherein X, Y, R, A, m and n have the same meanings as defined herein,which may be then subjected to a reaction such as halogenation oralkylsulfonylation in the usual manner to obtain the compoundrepresented by the formula (VIII-a) or (VIII-c):

wherein X, Y, R, A, m, n and L³ have the same definitions as above.

Representative examples of the compounds of the formula (VIII) andformula (VIII-b), respectively, in the preparation method (e) include:1-[3-chloro-4-(chloromethyl)phenyl]-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine;4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzylmethansulfonate;1-[3-bromo-4-(chloromethyl)phenyl]-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidineand the like.

The compounds of the formula (IX), which are the starting materials inthe preparation method (e), are well known compounds and representativeexamples include: acetoamide; propionamide; benzamide;2-chlorobenzamide; 3-chlorobenzamide; 4-chlorobenzamide and the like.

In performing the preparation method (e), for example, 1 mole of thecompound of the formula (VIII) or formula (VIII-b) may be reacted with 1to 3 moles of the formula (IX) in the presence of base in a diluent(e.g. THF) to obtain the corresponding compound of the formula (I) orformula (Ia).

The compounds of the formula (X), or formula (X-a) which are thestarting materials in the preparation method (f), are novel compound andmay be obtained by reacting a compound of formula (VIII) or formula(VI-b) with a compound R⁵—NH₂ (XXI) wherein R₅ has the same meanings asdefined herein.

The compounds of the formula (X) or formula (X-a) wherein l is 1 may bealso synthesized by the alternative method comprising reacting acompound of above formula (II) with a compound represented by theformula (XXII):

wherein Y, A, R³, R⁴, n and L¹ have the same meanings as defined herein,to obtain the compound represented by the formula (XXIII) or formula(XXIII-a):

wherein X, Y, R, A, m, n, R³ and R⁴ have the same meanings as definedherein, which is then reacted according to Gabriel synthetic reaction.

The compounds of above formula (XXII) are known compounds and include:2-(4-bromobenzyl)-1H-isoindole-1,3(2H)-dione;2-(4-bromo-2-nitrobenzyl)-1H-isoindole-1,3(2H)-dione;2-(4-iodobenzyl)-1H-isoindole-1,3(2H)-dione;2-(4-iodo-2-nitrobenzyl)-1H-isoindole-1,3(2H)-dione;2-(2-chloro-4-iodobenzyl)-1H-isoindole-1,3(2H)-dione.

The compounds of the formula (X) or formula (X-a) wherein R³, R⁴ and R⁵represent hydrogen may be easily synthesized by the alternative methodcomprising usual reduction reaction of the nitrile compound representedby the formula (XXIV) or formula (XXI-a):

wherein X, Y, R, m and n have the same meanings as defined herein.

The compounds of above formula (XXIV) or formula (XXIV-a) are novelcompounds and may be obtained as shown in the synthetic example 8described below.

Representative examples of the compounds of the formula (X) and formula(X-a), respectively, in the preparation method (f) include:1-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methanamine;1-{2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methanamine and the like.

The compounds of the formula (XI), which are the starting materials inthe preparation method (f), are well known compounds, and the specificexamples include: acetyl chloride; propionyl chloride; benzoyl chloride;2-chlorobenzoyl chloride; 3-chlorobenzoyl chloride; 4-chlorobenzoylchloride; nicotinoylchloride hydrochloride and the like.

In performing the preparation method (f), for example, 1 mole of thecompound of the formula (X) formula (X-a) may be reacted with 1 to 3moles of the formula (XI) in the presence of base in a diluent (e.g.THF) to obtain the corresponding compound of the formula (I) or formula(Ia).

The compounds of the formula (Ic) or formula (Ig), which are thestarting materials in the preparation method (g), are encompassed in theformula (I) or formula (Ia) of the present invention obtained by abovepreparation method (e) or (f).

The compounds of the formula (XII), which are the starting materials arewell known and the specific examples include iodomethane, iodoethane,acetyl chloride and the like.

In performing the preparation method (g), for example, 1 mole of thecompound of the formula (Ic) or formula (Ig) may be reacted with 1 to 3moles of the formula (XII) in the presence of base in a diluent (e.g.THF) to obtain the corresponding compound of the formula (I) or formula(Ia).

The compounds of the formula (XIII) or formula (XIII-a), which are thestarting materials in the preparation method (h), are novel compoundsand may be synthesized by the method described below.

More specifically, the compound of above formula (II) is reacted with acompound represented by the formula (XXV) or formula (XXV-a):

wherein Y, A, n and L¹ have the same meanings as defined herein, toobtain a compound represented by the formula (XXVI) or formula (XXVI-a):

wherein X, Y, R, A, m and n have the same meanings as defined herein,which is then reduced to obtain the compound of the formula (XIII) orformula (XIII-a).

The specific examples of compounds of formula (XXV) and formula (XXV-a)include: 2-fluoro-4-nitrobenzene; 2-bromo-4-nitrobenzene;2-iodo-4-nitrobenzene; 2-bromo-4-fluoronitrobenzene;4-fluoro-2-methylnitrobenzene and the like.

Representative examples of the compounds of the formula (XIII) andformula (XIII-a), respectively, in the preparation method (h) include:4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]aniline;2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]aniline and the like.

Dialkoxy tetrahydrofurans, which are the starting materials in thepreparation method (h), are known compounds and the specific examplesinclude: 2,5-dimethoxytetrahydrofuran; 2,5-diethoxytetrahydrofuran andthe like.

In performing above preparation method (h), for example, 1 mole of thecompound of the formula (XIII) or formula (XIII-a) may be reacted with 1to 5 moles of 2,5-dimethoxytetrahydrofuran in a diluent (e.g. aceticacid) to obtain the corresponding compound of the formula (I) or formula(Ia) of the present invention.

In the preparation method (h), said reaction, when using1,2-diformylhydrazine, may be performed in the presence of base andtrialkylhalosilane.

The examples of the base may include organic bases such astriethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine,N,N-dimethylaniline, N,N-diethylaniline,4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine,diazabicycloundecene, diazabicyclooctane, imidazole etc.

Representative examples of trialkylhalosilanes include:trimethylchlorosilane; triethylchlorosilane; trimethylbromosilane andthe like.

In performing the preparation method (h), 1 mole of the compound of theformula (XIII) or formula (XIII-a) may be reacted with 1 to 5 moles of1,2-diformylhydrazine, 1 to 10 moles of base and 1 to 25 moles oftrialkylhalosilane in great excess amount of pyridine to obtain thedesired corresponding compound of the formula (I) or formula (Ia).

In the case of the reaction of sodium azide with trialkyl orthoformatein the preparation method (h), the examples of trialkyl orthoformatesmay include trimethyl orthoformate and triethyl orthoformate and thelike.

In performing the preparation method (h), 1 mole of the compound of theformula (XIII) or formula (XIII-a) may be reacted with 1 to 3 moles ofsodium azide and 1 to 10 moles of trialkyl orthoformate in a diluent(e.g. acetic acid) to obtain the corresponding compound of the formula(I) or formula (Ia) of the invention.

The compounds of the formula (XIV) or formula (XIV-a), which are thestarting materials in the preparation method (i), are novel compoundsand may be synthesized by the method described below. More specifically,the compound of above formula (XIII) or formula (XII-a) is subjected toSandmeyer's reaction, which is known in the field of organic chemistry,followed by reduction to obtain the compound of the formula (XIV) orformula (XIV-a).

Representative examples of the compounds of the formula (XIV) andformula (XIV-a), respectively may include:3-(3,5-dichlorophenyl)-1-(4-hydrazinophenyl)-3-(trifluoromethyl)pyrrolidine;3-(3,5-dichlorophenyl)-1-(4-hydrazino-3-methylphenyl)-3-(tri-fluoromethyl)pyrrolidineand the like.

2,5-Dialkoxy tetrahydrofurans, which are used as starting material inthe preparation method (i), are known compounds and representativeexamples include: 1,1,3,3-tetramethoxypropane;1,1,3,3-tetraethoxypropane and the like.

In performing above preparation method (i), for example, 1 mole of thecompound of the formula (XIV) or formula (XIV-a) may be reacted with 1to 5 moles of 1,1,3,3-tetraalkoxypropane with, if desired, addition ofcatalytic amount of acid such as sulfuric acid in a diluent (e.g.ethanol) to obtain the corresponding compound of the formula (I) orformula (Ia) of the invention.

The compounds of the formula (XV) or formula (XV-a), which are thestarting material in the preparation method (j), are novel compounds andmay be synthesized by the method described below. More specifically, thecompound of above formula (II) is reacted with a compound represented bythe formula (XXVII) or formula (XXVII-a)

wherein Y, A, n and L¹ have the same meanings as defined herein, toobtain the compound of the formula (XV) or formula (XV-a).

The specific examples of compounds of above formula (XXVII) and formula(XXVII-a), respectively, include: 2-fluoro-5-iodobenzonitrile;5-bromo-2-fluorobenzonitrile; 1-chloro-4-iodo-2-nitrobenzene;1,4-dibromobenzene; 1,4-diiodo benzene and the like.

Representative examples of the compounds of the formula (XV) and formula(XV-a), respectively in the preparation method (j) may include:5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-fluorobenzonitrile;5-{3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)pyrrolidin-1-yl}-2-fluorobenzonitrile and the like.

Many of the compounds represented by the formula G2-H, G3-H, G4-H, G5-G,G6-H, G8-H, G9-H, which are the starting materials in the preparationmethod (j), are known compounds and the specific examples may include:1H-imidazole; 1H-pyrazole; 4-methyl-1H-pyrazole; 4-fluoro-1H-pyrazole;4-chloro-1H-pyrazole; 4-bromo-1H-pyrazole; 4-iodo-1H-pyrazole;4-nitro-1H-pyrazole; 4-methyl-1H-pyrazole;3-trifluoromethyl-1H-pyrazole; 4-trifluoromethyl-1H-pyrazole;4-cyano-1H-pyrazole; 1H-1,2,3-triazole; 1H-1,2,4-triazole; 1H-tetrazole;5-methyl-1H-tetrazole; 5-(methylthio)-1H-tetrazole and the like.

In performing the preparation method (j), for example, 1 mole of thecompound of the formula (XV) or formula (XV-a) may be reacted with 1 to3 moles of G6-H in the presence of 1 to 3 moles of base in a diluent(e.g. DMF) to obtain the corresponding compound of the formula (I) orformula (Ia) of the invention.

In preparation methods of the compounds of the formula (I) or formula(Ia) of the present invention, novel materials among the compounds whichare the raw materials (starting materials and intermediates) can becollectively represented by the formula described below.

Formula (II-a)

wherein X has the same meanings as defined herein, T¹ representshydrogen or benzyl, Hal-R represents haloalkyl and p represents 1, 2, 3,4 or 5.

Formula (XVI-a)

wherein T² and T³ each independently represent alkyl.

Compounds of Formula (XXVII) or compounds of formula (XXVIII-a)

wherein X, Y, R, A, m and n has the same definition as above, T⁴represents:

cyano, amino or nitro, R⁸, L², L³, R³, R⁴ and R⁵ have the same meaningsas defined herein.

The compounds according to the present invention have potentinsecticidal and acaricidal activity. Therefore, the compoundsrepresented by formula (I) or formula (Ia) of the present invention canbe used as insecticides and/or acaricides. They are particularly usefulin the agricultural field. The compounds according to the presentinvention also exert an appropriate controlling effect against harmfulinsects without phytotoxicity against cultured plants. In addition, thecompounds of the present invention can be used for controlling a widevariety of pests including, for example, harmful sucking insects, bitinginsects and other plant-parasitic pests, stored grain pests and hygienicpests as well as pests in the veterinary field and can be applied fortheir control, in particular eradication and extermination. Therefore,the present invention also encompasses a method for combating harmfulpests.

Such pest insects include for example

Beetles, such as adzuki bean beetle (Callosobruchus Chinensis), maizeweevil (Sitophilus zeamais), red flour beetle (Tribolium Castaneum),large 28-spotted lady beetle (Epilachna vigintioctomaculata), barleywireworm (Agriotes fuscicollis), soy bean beetle (Anomala rufocuprea),colorado potato beetle (Leptinotarsa decemlineata), diabrotica(Diabrotica spp.), Japanese pine sawyer (Monochamus alternatus), ricewater weevil (Lissorhoptrus oryzophilus), powderpost beetle (Lyctusbruneus), cucurbit leaf beetle (Aulacophora femoralis).

Lepidopteran pests, such as gypsy moth (Lymantria dispar), tentcaterpillar (Malacosoma neustria), small white (Pieris rapae), commoncutworm (Spodoptera litura), cabbage moth (Mamestra brassicae), StripedRice Borer (Chilo suppressalis), corn borer (Pyrausta nubilalis), driedcurrant moth (Ephestia cautella), summer fruit tortrix moth (Adoxophyesorana), codling moth (Carpocapsa pomonella), common cutworm moth(Agrotis fucosa), wax moth (Galleria mellonella), diamondback moth(Plutella maculipennis), Heliothis (Heliothis virescens), citrusleafminer (Phyllocnistis citrella).

Hemipterous pests, such as green rice leafhopper (Nephotettixcincticeps), brown planthopper (Nilaparvata lugens), comstock mealybug(Pseudococcus comstocki), arrowhead scale (Unaspis yanonensis),Momoaka-aburamusi (Myzus persicas), Green apple aphid (Aphis pomi),cotton aphid (Aphis gossypii), turnip aphid (Phopalosiphumpseudobrassicas), Nashi-gunbai (Stephanitis nashi), Nazara (Nazaraspp.), greenhouse whitefly (Trialeurodes vaporariorm), Pshylla (Pshyllaspp.).

Thripid pests, such as melon thrips (Thrips palmi), western flower thrip(Frankliniella occidentalis).

Orthopteran pests, such as german Cockroach (Blatella germanica),american cockroach (Periplaneta americana), mole cricket (Gryllotalpaafricana), migratory locust (Locusta migratoria migratoriaodes)

Isoptera pests, such as Japanese subterranean termite (Reticulitermessperatus), termite (Coptotermes formosanus);

Dipterous pests, such as house fly (Musca domestica), yellow fevermosquito (Aedes aegypti), bean seed fly (Hylemia platura), Aka-ie-ka(Culex pipiens), Sina-hamadara-ka (Anopheles sinensis), kodaka-aka-ie-ka(Culex tritaeniorhychus), american serpentine leafminer (Liriomyzatrifolii).

Mites, such as Nise-nami-hadani (Tetranychus cinnabarinus), Nami-ha-dani(Tetrahychus urticae), citrus red mite (Panonychus citri), pink citrusrust mite (Aculops pelekassi), Tarsonemus (Tarsonemus spp.).

Nematode pests, such as sweet potato root-knot nematode (Meloidogyneincognita), pine wood nematode (Bursaphelenchus lignicolus Mamiya etKiyohara), rice nematode (Aphelenchoides besseyi), soybean cyst nematode(Heterodera glycines), meadow nematode (Pratylenchus spp.).

Additionally, the compounds according to the invention, in combinationwith good plant tolerance and favourable toxicity to warm-bloodedanimals and being tolerated well by the environment, are suitable forprotecting plants and plant organs, for increasing the harvest yields,for improving the quality of the harvested material and for controllinganimal pests, in particular insects, arachnids, helminths, nematodes andmolluscs, which are encountered in agriculture, in horticulture, inanimal husbandry, in forests, in gardens and leisure facilities, in theprotection of stored products and of materials, in the hygiene andanimal health sector. They may be preferably employed as plantprotection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Thepests which can be combated by using the compounds and compositionsaccording to the invention further include inter alia:

From the order of the Anoplura (Phthiraptera), for example, Damaliniaspp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectesspp.

From the class of the Arachnida, for example, Acarus siro, Aceriasheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp.,Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri,Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp.,Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychusspp., Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora,Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp.,Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp.,Tarsonemus spp., Tetranychus spp., Vasates lycopersici.

From the class of the Bivalva, for example, Dreissena spp.

From the order of the Chilopoda, for example, Geophilus spp., Scutigeraspp.

From the order of the Coleoptera, for example, Acanthoscelides obtectus,Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis,Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp.,Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus,Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp.,Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchuslapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinuscubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans,Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosternaconsanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus,Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha,Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptushololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchussulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp.,Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinusspp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp.,Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor,Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrusspp.; as well as Callosobruchus Chinensis, Sitophilus zeamais, TriboliumCastaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomalarufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamusalternatus, Lissorhoptrus oryzophilus, Lyctus bruneus, and Aulacophorafemoralis.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata,Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp.,Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fanniaspp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp.,Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp.,Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanusspp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.; as well as Muscadomestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anophelessinensis, Culex tritaeniorhychus and Liriomyza trifolii.

From the class of the Gastropoda, for example, Arion spp., Biomphalariaspp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp.,Oncomelania spp., Succinea spp.

From the class of the helminths, for example, Ancylostoma duodenale,Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp.,Ascaris lumbricoides, Ascaris spp., Brugia malayi, Brugia timori,Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.,Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum,Dracunculus medinensis, Echinococcus granulosus, Echinococcusmultilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp.,Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa,Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocercavolvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp.,Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp.,Taenia saginata, Taenia solium, Trichinella spiralis, Trichinellanativa, Trichinella britovi, Trichinella nelsoni, Trichinellapseudopsiralis, Trichostrongulus spp., Trichuris trichiura, Wuchereriabancrofti.

It is furthermore possible to control protozoa, such as Eimeria.

From the order of the Heteroptera, for example, Anasa tristis,Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida,Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis,Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistusspp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisaspp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae,Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp.,Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergellasingularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatomaspp.

From the order of the Homoptera, for example, Acyrthosipon spp.,Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobusbarodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui,Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis,Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani,Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicorynebrassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacunalanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii,Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola,Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp.,Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp.,Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccusspp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelisbilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterusarundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphaxstriatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi,Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari,Metcalfiella spp., Metopolophium dirhodum, Monellia costalis,Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettixspp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga,Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp.,Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodonhumuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp.,Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcusspp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp.,Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus,Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina,Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp.,Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp.,Unaspis spp., Viteus vitifolii.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Isopoda, for example, Armadillidium vulgare,Oniscus asellus, Porcellio scaber.

From the order of the Isoptera, for example, Reticulitermes spp.,Odontotermes spp.; as well as Reticulitermes speratus and Coptotermesformosanus.

From the order of the Lepidoptera, for example, Acronicta major, Aedialeucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathrabrassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana,Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp.,Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Eariasinsulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp.,Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp.,Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella,Laphygma spp., Lithocolletis blancardella, Lithophane antennata,Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestrabrassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae,Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella,Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp.,Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesiagemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana,Trichoplusia spp.; as well as Lymantria dispar, Malacosoma neustria,Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis,Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsapomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis,Heliothis virescens and Phyllocnistis citrella.

From the order of the Orthoptera, for example, Acheta domesticus, Blattaorientalis, Gryllotalpa spp., Leucophaea maderae, Locusta spp.,Melanoplus spp., Schistocerca gregaria; as well as Blattella germanica,Periplaneta americana, Gryllotalpa africana and Locusta migratoriamigratoriaodes.

From the order of the Siphonaptera, for example, Ceratophyllus spp.,Xenopsylla cheopis.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanoptera, for example, Baliothrips biformis,Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothripsfemoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothripsspp., Taeniothrips cardamoni, Thrips spp.; as well as Thrips palmi andFrankliniella occidentalis.

From the order of Hemiptera, for example, Nephotettix cincticeps,Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzuspersicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas,Stephanitis nashi, Nazara spp., Trialeurodes vaporariorm and Pshyllaspp.;

From the order of the Thysanura, for example, Lepisma saccharina.

The phytoparasitic nematodes include, for example, Anguina spp.,Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchusdipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp.,Longidorus spp., Meloidogyne spp., Radopholus similis, Rotylenchus spp.,Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulussemipenetrans, Xiphinema spp.; as well as Meloidogyne incognita,Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi,and Heterodera glycines and Pratylenchus spp.

Mites include, for example, Tetranychus cinnabarinus, Tetranychusurticae, Panonychus citri, Aculops pelekassi and Tarsonemus spp. orMites, such as Ornithodoros spp., Ixodes spp., Boophilus spp. and thelike.

In the present invention, substances having insecticidal effects againstvermins encompassing all of such pests are referred to as insecticides.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides,safeners, growth regulators or agents to improve plant properties, or asmicrobicides, for example as fungicides, antimycotics, bactericides,viricides (including agents against viroids) or as agents against MLO(mycoplasma-like organisms) and RLO (rickettsia-like organisms). Ifappropriate, they can also be employed as intermediates or precursorsfor the synthesis of other active compounds.

In the veterinary field, the novel compounds of the invention can beeffectively used to various harmful animal parasites (endoparasites andectoparasites), including insects and worms.

Examples of such animal parasites may include the following vermins:insects, such as bot fly (Gastrophilus spp.), stable fly (Stomoxysspp.), biting louse (Trichodectes spp.), Rhodnius (Rhodnius spp.),inu-nomi (Ctenocephalides canis), bedbug (Cimx lecturius), neko-nomi(Ctenocephalides felis), sheep blowfly (Lucilia cuprina) and the like.

As already mentioned before, in the veterinary fields, i.e. in the fieldof veterinary medicine, the active compounds according to the presentinvention are active against animal parasites, in particularectoparasites or endoparasites. The term endoparasites includes inparticular helminths, such as cestodes, nematodes or trematodes, andprotozoae, such as coccidia. Ectoparasites are typically and preferablyarthropods, in particular insects such as flies (stinging and licking),parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; oracarids, such as ticks, for examples hard ticks or soft ticks, or mites,such as scab mites, harvest mites, bird mites and the like.

These parasites include:

From the order of the Anoplurida, for example Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.;particular examples are: Linognathus setosus, Linognathus vituli,Linognathus ovillus, Linognathus oviformis, Linognathus pedalis,Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinuseurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculushumanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotescapillatus.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.; particular examples are: Bovicolabovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectescanis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis,Werneckiella equi.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitraspp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp.,Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp.,Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Luciliaspp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.,Melophagus spp., Rhinoestrus spp., Tipula spp.; particular examples are:Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anophelesgambiae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozonapluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Fanniacanicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludosa,Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomuspapatasi, Phlebotomus longipalpis, Odagmia ornata, Wilhelmia equina,Boophthora erythrocephala, Tabanus bromius, Tabanus spodopterus, Tabanusatratus, Tabanus sudeticus, Hybomitra ciurea, Chrysops caecutiens,Chrysops relictus, Haematopota pluvialis, Haematopota italica, Muscaautumnalis, Musca domestica, Haematobia irritans irritans, Haematobiairritans exigua, Haematobia stimulans, Hydrotaea irritans, Hydrotaeaalbipuncta, Chrysomya chloropyga, Chrysomya bezziana, Oestrus ovis,Hypoderma bovis, Hypoderma lineatum, Przhevalskiana silenus, Dermatobiahominis, Melophagus ovinus, Lipoptena capreoli, Lipoptena cervi,Hippobosca variegata, Hippobosca equina, Gasterophilus intestinalis,Gasterophilus haemorroidalis, Gasterophilus inermis, Gasterophilusnasalis, Gasterophilus nigricornis, Gasterophilus pecorum, Braula coeca.

From the order of the Siphonapterida, for example Pulex spp.,Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.;particular examples are: Ctenocephalides canis, Ctenocephalides felis,Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of the Heteropterida, for example Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp. (e.g. Suppellalongipalpa).

From the subclass of the Acari (Acarina) and the orders of the Meta- andMesostigmata, for example Argas spp., Ornithodorus spp., Otobius spp.,Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp Dermacentorspp., Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalusspp. (the original genus of multi host ticks) Ornithonyssus spp.,Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp.,Varroa spp., Acarapis spp.; particular examples are: Argas persicus,Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipicephalus(Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus,Rhipicephalus (Boophilus) annulatus, Rhipicephalus (Boophilus)calceratus, Hyalomma anatolicum, Hyalomma aegypticum, Hyalommamarginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus,Ixodes hexagonus, Ixodes canisuga, Ixodes pilosus, Ixodes rubicundus,Ixodes scapularis, Ixodes holocyclus, Haemaphysalis concinna,Haemaphysalis punctata, Haemaphysalis cinnabarina, Haemaphysalisotophila, Haemaphysalis leachi, Haemaphysalis longicorni, Dermacentormarginatus, Dermacentor reticulatus, Dermacentor pictus, Dermacentoralbipictus, Dermacentor andersoni, Dermacentor variabilis, Hyalommamauritanicum, Rhipicephalus sanguineus, Rhipicephalus bursa,Rhipicephalus appendiculatus, Rhipicephalus capensis, Rhipicephalusturanicus, Rhipicephalus zambeziensis, Amblyomma americanum, Amblyommavariegatum, Amblyomma maculatum, Amblyomma hebraeum, Amblyommacajennense, Dermanyssus gallinae, Ornithonyssus bursa, Ornithonyssussylviarum, Varroa jacobsoni.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.; particularexamples are: Cheyletiella yasguri, Cheyletiella blakei, Demodex canis,Demodex bovis, Demodex ovis, Demodex caprae, Demodex equi, Demodexcaballi, Demodex suis, Neotrombicula autumnalis, Neotrombicula desaleri,Neoschongastia xerothermobia, Trombicula akamushi, Otodectes cynotis,Notoedres cati, Sarcoptis canis, Sarcoptes bovis, Sarcoptes ovis,Sarcoptes rupicaprae (=S. caprae), Sarcoptes equi, Sarcoptes suis,Psoroptes ovis, Psoroptes cuniculi, Psoroptes equi, Chorioptes bovis,Psoergates ovis, Pneumonyssoidic Mange, Pneumonyssoides caninum,Acarapis woodi.

The active compounds according to the invention are also suitable forcontrolling arthropods, helminths and protozoae, which attack animals.The control of arthropods is preferred. The control of insects isparticularly preferred. Equally, the control of acarids is particularlypreferred.

Animals which may be treated to control the parasites include birds,insects and in particular mammals. Animals include agriculturallivestock such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffaloes, rabbits, chickens, fur-bearing animals,turkeys, ducks, geese, cultured fish, honeybees. Moreover, animalsinclude domestic animals—also referred to as companion animals—such as,for example, dogs, cats, ferrets, cage birds, aquarium fish, reptilesand what are known as experimental animals such as, for example,hamsters, guinea pigs, rats and mice.

By controlling these arthropods, helminths and/or protozoae, it isintended to reduce deaths and improve performance (in the case of meat,milk, wool, hides, eggs, honey and the like) and health of the hostanimal, so that more economical and simpler animal keeping is madepossible by the use of the active compounds according to the invention.

For example, it is desirable to prevent or interrupt the uptake of bloodby the parasites from the hosts (when applicable). Also, controlling theparasites may help to prevent the transmittance of infectious agents.

The term “controlling” as used herein with regard to the veterinaryfield, means that the active compounds are effective in reducing theincidence of the respective parasite in an animal infected with suchparasites to innocuous levels. More specifically, “controlling”, as usedherein, means that the active compound is effective in killing therespective parasite, inhibiting its growth, or inhibiting itsproliferation.

The active compounds of the present invention, when used asinsecticides, may be formed into conventional formulation forms. Suchformulation forms include, for example, solutions, emulsions, wettablepowders, water dispersible granules, suspensions, powders, foams,pastes, tablets, granules, aerosols, active compound-impregnated naturaland synthetic substances, microcapsules, seed coating agents,formulations used with burning device (burning devices include, forexample, fumigation and smoking cartridges, cans and coils) and UVL[cold mist, warm mist].

The active compounds of the formula (I) or formula (Ia) of the inventionmay be present in the commercially useful formulations and usage formsprepared from their formulations, as a mixed formulation form with otheractive compounds such as insecticides, toxic baits, bactericides,acaricides, nematocides, fungicides, growth regulating agents,herbicides and the like. Above mentioned insecticides may include, forexample, organophosphorus agents, carbamate agents, carboxylate chemicalagents, chlorohydrocarbon type chemical agents, insecticidal substancesproduced by microorganisms and the like.

These formulations may be prepared by the method known per se. Forexample, they can be prepared by mixing the active compounds togetherwith spreading agents, i.e. liquid diluents or carriers; Liquefied gasdiluents or carriers; solid diluents or carriers, and, optionally,surfactants i.e. emulsifiers and/or dispersants and/or foam formingagents.

When water is used as a spreading agent, for example organic solventsmay be used as an auxiliary solvent.

Liquid diluents or carriers may include, for example, aromatichydrocarbons (e.g. xylene, toluene, alkylnaphthalene etc.), chlorinatedaromatic or chlorinated aliphatic hydrocarbons (e.g. chlorobenzens,ethylene chlorides, methylene chlorides etc.), aliphatic hydrocarbons(e.g. cyclohexanes or paraffins (e.g. mineral oil fractions)), alcohols(e.g. butanol, glycol and ethers or esters thereof etc.), ketones (e.g.acetone, methylethylketone, methylisobutylketone, cyclohexanone etc.),strong polar solvents (e.g. dimethylformamide, dimethylsulfoxide etc.),water and the like.

Liquefied gas diluents or carriers may include substances which exist asgas at ambient temperature and normal pressure, for example aerosolpropellants such as furan, propane, nitrogen gas, carbon dioxide,halogenated hydrocarbons.

Solid diluents may include, for example, crushed natural minerals (e.g.kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite ordiatom earth etc.), crushed synthetic minerals (e.g. highly-dispersivesilic acid, alumina, silicate etc.) and the like.

Solid carriers for granules may include, for example, crushed andfractionated rocks (e.g. calcite, marble, pumice stone, sepiolite,dolomite etc.), synthetic granules of inorganic or organic powders, fineparticles of organic materials (e.g. sawdust, coconut shells, corncob,stalk of Indian weed etc.).

Emulsifiers and/or foams may include, for example, nonionic or anionicemulsifiers (e.g. polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers (e.g. alkylarylpolyglycol ether), alkyl sulfonates,alkyl sulfates, aryl sulfonates etc.), albumin hydrolyzed products andthe like.

Examples of dispersants include, for example, lignin sulfite wasteliquor, methylcellulose and the like.

Adhesive agents may also be used for the formulations (powders,granules, emulsions), such as carboxymethylcellulose, natural orsynthetic polymers (e.g. acacia, polyvinyl alcohols, polyvinyl acetatesetc.) and the like.

Colorants may be used, such as inorganic pigments (e.g. ferric oxide,titanic oxide, Prussian blue etc.), organic pigments (e.g. alizarindyes, azo dyes or metallophthalocyanine dyes etc.) as well as traceelements (e.g. salts of iron, manganese, boron, copper, cobalt,molybdenum or zinc etc.).

Generally such formulations may contain the active compounds describedabove in a range from 0.1 to 95% by weight, preferably 0.5 to 90% byweight.

The compounds according to the present invention may be used in ordinarymanners suitable for their application forms. It is understood that thecompounds according to the invention can also be present in compositionscontaining further ingredients, such as auxiliaries or activeingredients.

The skilled person will choose a suitable ingredient among those namedherein and known in the art and which are supposed to enhance a propertywhich is considered being favorable in view of the intended applicationand use.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and geneticengineering methods or by combinations of these methods, including thetransgenic plants and including the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodas meaning all parts and organs of plants above and below the ground,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offshoots and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, habitat or storage space by thecustomary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on, injecting and, in thecase of propagation material, in particular in the case of seed, also byapplying one or more coats.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andparts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineeringmethods, if appropriate in combination with conventional methods(Genetically Modified Organisms), and parts thereof, are treated. Theterms “parts”, “parts of plants” and “plant parts” have been explainedabove.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are understood as meaning plants having novelproperties (“traits”) which have been obtained by conventional breeding,by mutagenesis or by recombinant DNA techniques. These can be cultivars,bio- or genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, higher quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possible,which exceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (obtained by geneticengineering) which are to be treated according to the invention includeall plants which, by virtue of the genetic modification, receivedgenetic material which imparts particularly advantageous, useful traitsto these plants. Examples of such traits are better plant growth,increased tolerance to high or low temperatures, increased tolerance todrought or to water or soil salt content, increased floweringperformance, easier harvesting, accelerated maturation, higher harvestyields, higher quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch traits are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peasand other vegetable varieties, cotton, tobacco, oilseed rape and alsofruit plants (with the fruits apples, pears, citrus fruits and grapes),and particular emphasis is given to maize, soya beans, potatoes, cotton,tobacco and oilseed rape. Traits that are emphasized in particular arethe increased defence of the plants against insects, arachnids,nematodes and slugs and snails by virtue of toxins formed in the plants,in particular those formed in the plants by the genetic material fromBacillus thuringiensis (for example by the genes CryIA(a), CryIA(b),CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF andalso combinations thereof) (referred to hereinbelow as “Bt plants”).Traits that are also particularly emphasized are the increased defenceof the plants against fungi, bacteria and viruses by systemic acquiredresistance (SAR), systemin, phytoalexins, elicitors and resistance genesand correspondingly expressed proteins and toxins. Traits that arefurthermore particularly emphasized are the increased tolerance of theplants to certain herbicidally active compounds, for exampleimidazolinones, sulphonylureas, glyphosate or phosphinotricin (forexample the “PAT” gene). The genes which impart the desired traits inquestion can also be present in combination with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya beans), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to plant cultivars having these genetic traits orgenetic traits still to be developed, which plant cultivars will bedeveloped and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds or compositionsaccording to the invention. The preferred ranges stated above for theactive compounds or compositions also apply to the treatment of theseplants. Particular emphasis is given to the treatment of plants with thecompounds or compositions specifically mentioned in the present text.

It has furthermore been found that the compounds according to theinvention also have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as preferred—butwithout any limitation:

Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendronspec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec. Dinoderus minutus;

Hymenopterons, such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus, Urocerus augur;

Termites, such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus;

Bristletails, such as Lepisma saccharina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cardboards, leather, wood and processed wood productsand coating compositions.

The ready-to-use compositions may, if appropriate, comprise furtherinsecticides and, if appropriate, one or more fungicides.

With respect to possible additional additives, reference may be made tothe insecticides and fungicides mentioned above.

The compounds according to the invention can likewise be employed forprotecting objects which come into contact with saltwater or brackishwater, in particular hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Furthermore, the compounds according to the invention, alone or incombinations with other active compounds, may be employed as antifoulingagents.

In domestic, hygiene and stored-product protection, the active compoundsare also suitable for controlling animal pests, in particular insects,arachnids and mites, which are found in enclosed spaces such as, forexample, dwellings, factory halls, offices, vehicle cabins and the like.They can be employed alone or in combination with other active compoundsand auxiliaries in domestic insecticide products for controlling thesepests. They are active against sensitive and resistant species andagainst all developmental stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleoptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix,Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

In the field of domestic insecticides, a combination with other suitableactive compounds, such as phosphoric esters, carbamates, pyrethroids,neonicotinoids, growth regulators or active compounds from other knownclasses of insecticides can be used and is especially preferable.

The compounds or compositions according to the invention, preferable intheir suitable application form, can be used in aerosols, pressure-freespray products, for example pump and atomizer sprays, automatic foggingsystems, foggers, foams, gels, evaporator products with evaporatortablets made of cellulose or polymer, liquid evaporators, gel andmembrane evaporators, propeller-driven evaporators, energy-free, orpassive, evaporation systems, moth papers, moth bags and moth gels, asgranules or dusts, in baits for scattering or in bait stations.

The compounds or compositions according to the invention areparticularly suitable for treating seed. A large part of the damage tocrop plants which is caused by pests occurs as early as when the seed isattacked during storage and after the seed is introduced into the soil,during and immediately after germination of the plants. This phase isparticularly critical since the roots and shoots of the growing plantare particularly sensitive and even minor damage can lead to the deathof the whole plant. Protecting the seed and the germinating plant by theuse of suitable compositions is therefore of particularly greatinterest.

The control of pests by treating the seed of plants has been known for along time and is subject-matter of continuous improvements. However, thetreatment of seed entails a series of problems which cannot always besolved in a satisfactory manner. Thus, it is desirable to developmethods for protecting the seed and the germinating plant which dispensewith the additional application of crop protection agents after sowingor after the emergence of the plants. It is furthermore desirable tooptimize the amount of active compound employed in such a way as toprovide maximum protection for the seed and the germinating plant fromattack by pests, but without damaging the plant itself by the activecompound employed. In particular, methods for the treatment of seedshould also take into consideration the intrinsic insecticidalproperties of transgenic plants in order to achieve optimum protectionof the seed and also the germinating plant with a minimum of cropprotection agents being employed.

The present invention therefore in particular also relates to a methodfor the protection of seed and germinating plants from attack by pests,by treating the seed with a composition according to the invention. Theinvention likewise relates to the use of the compositions according tothe invention for the treatment of seed for protecting the seed and theresulting plant from pests. Furthermore, the invention relates to seedwhich has been treated with a composition according to the invention soas to afford protection from pests.

One of the advantages of the present invention is that the particularsystemic properties of the compositions according to the invention meanthat treatment of the seed with these compositions not only protects theseed itself, but also the resulting plants after emergence, from pests.In this manner, the immediate treatment of the crop at the time ofsowing or shortly thereafter can be dispensed with.

Furthermore, it must be considered as advantageous that the compounds orcompositions according to the invention can also be employed inparticular in transgenic seed, the plants arising from this seed beingcapable of expressing a protein directed against pests. By treating suchseed with the compositions according to the invention, certain pests canbe controlled merely by the expression of the, for example, insecticidalprotein, and additionally be protected by the compositions according tothe invention against damage.

The compounds or compositions according to the invention are suitablefor protecting seed of any plant variety as already mentioned abovewhich is employed in agriculture, in the greenhouse, in forests or inhorticulture. In particular, this takes the form of seed of maize,peanut, canola, oilseed rape, poppy, soya beans, cotton, beet (forexample sugar beet and fodder beet), rice, sorghum and millet, wheat,barley, oats, rye, sunflower, tobacco, potatoes or vegetables (forexample tomatoes, cabbage plants). The compositions according to theinvention are likewise suitable for treating the seed of fruit plantsand vegetables as already mentioned above. The treatment of the seed ofmaize, soya beans, cotton, wheat and canola or oilseed rape is ofparticular importance.

As already mentioned above, the treatment of transgenic seed with acomposition according to the invention is also of particular importance.This takes the form of seed of plants which, as a rule, comprise atleast one heterologous gene which governs the expression of apolypeptide with in particular insecticidal properties. In this context,the heterologous genes in transgenic seed may be derived frommicroorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia,Trichoderma, Clavibacter, Glomus or Gliocladium. The present inventionis particularly suitable for the treatment of transgenic seed whichcomprises at least one heterologous gene originating from Bacillus sp.and whose gene product shows activity against the European corn borerand/or the corn root worm. It is particularly preferably a heterologousgene derived from Bacillus thuringiensis.

In the context of the present invention, the composition according tothe invention is applied to the seed either alone or in a suitableformulation. Preferably, the seed is treated in a state which is stableenough to avoid damage during treatment. In general, the seed may betreated at any point in time between harvest and sowing. The seedusually used has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active compounds which may have phytotoxic effects at certainapplication rates.

The active compounds of the present invention, when used againsthygienic pests and stored grain pests, have a good stability to alkalion calcareous substances and also show an excellent residual activity inwood and soil.

In addition, the active compounds of the formula (I) or formula (Ia) ofthe invention may be present as a mixed formulation with synergists andsuch formulations and usage forms may include commercially usefulformulations and forms. Such synergists, which are not necessarilyactive per se, are compounds enhancing the action of the activecompounds.

Generally, when used for the treatment of animals the active compoundsaccording to the invention can be applied directly. Preferably they areapplied as pharmaceutical compositions which may containpharmaceutically acceptable excipients and/or auxiliaries which areknown in the art.

In the veterinary field and in animal keeping, the active compounds areapplied (=administered) in the known manner by enteral administration inthe form of, for example, tablets, capsules, drinks, drenches, granules,pastes, boluses, the feed-through method, suppositories; by parenteraladministration, such as, for example, by injections (intramuscular,subcutaneous, intravenous, intraperitoneal and the like), implants, bynasal application, by dermal application in the form of, for example,bathing or dipping, spraying, pouring-on and spotting-on, washing,dusting, and with the aid of active-compound-comprising shaped articlessuch as collars, ear tags, tail tags, limb bands, halters, markingdevices and the like. The active compounds may be formulated as shampooor as suitable formulations usable in aerosols, unpressurized sprays,for example pump sprays and atomizer sprays.

When used for livestock, poultry, domestic animals and the like, theactive compounds according to the present invention can be applied asformulations (for example powders, wettable powders [“WP”], emulsions,emulsifiable concentrates [“EC”], flowables, homogeneous solutions andsuspension concentrates [“SC”]) which comprise the active compounds inan amount of from 1 to 80% by weight, either directly or after dilution(e.g. 100- to 10 000-fold dilution), or else as a chemical bath.

When used in the veterinary field the active compounds according to theinvention may be used in combination with suitable synergists or otheractive compounds, such as for example, acaricides, insecticides,anthelmintics, anti-protozoal drugs.

The present invention is more specifically illustrated by means of thefollowing examples. However the present invention should not be limitedonly to these examples.

SYNTHETIC EXAMPLE 1 Synthesis ofN-{4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-methylbenzyl}acetamide(No. 3-11)

Sodium tert-butoxide (0.3 g), Tris(dibenzylidene acetone)dipalladium(0)(chloroform adduct)(0.04 g) and xantphos (0.07 g) was added to thesolution of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (0.59g) and N-(4-bromo-2-methylbenzyl)acetamide (0.5 g) in toluene underargon atmosphere, and the mixture was heated with stirring at 80° C. for5 hours. The reaction solution was diluted with t-butylmethylether andthen washed with water and brine. The organic layer was dried overanhydrous magnesium sulfate. The solvent was distilled away under thereduced pressure, and the residue was then purified by silica gelchromatography to yieldN-{4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-methylbenzyl}acetamide(0.6 g). ¹H-NMR (CDCl₃) δ: 2.13-2.18 (6H, m), 2.51-2.53 (1H, m),2.81-2.83 (1H, m), 3.45-3.56 (2H, m), 3.75-3.78 (1H, m), 4.01-4.04 (1H,m), 4.25 (1H, s), 4.57 (1H, s), 6.40-6.44 (2H, m), 6.93-6.96 (1H, m),7.30-7.38 (3H, m)

SYNTHETIC EXAMPLE 2 Synthesis of4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitro-N-(pyridin-2-ylmethyl)benzamide (No. 1-16)SYNTHETIC EXAMPLE 2-1 Synthesis of1-benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidine (No.5-11)

To the solution of 1,3-dichloro-5-[1-trifluoromethyl)vinyl]benzene (6.1g) and N-benzyl-1-methoxy-N-[(trimethylsilyl)methyl]methanamine (5.0 g)in dichloromethane was added dropwise the solution of trifluoroaceticacid (0.24 g) in dichloromethane while cooling with ice. On completionof the dropwise addition, the mixture was warmed to room temperature andstirred for 3 hours. The solution was concentrated under the reducedpressure, and the residue was then diluted with t-butylmethylether. Thesolution was washed with saturated sodium bicarbonate water and driedover anhydrous magnesium sulfate. After the drying agent was filteredoff, the solvent was distilled away under the reduced pressure, and theresidue was then purified by silica gel chromatography to yield1-benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidine (5.7 g).¹H-NMR (CDCl₃) δ: 2.27-2.36 (1H, m), 2.53-2.62 (1H, m), 2.69-2.83 (2H,m), 3.08 (2H, dd), 3.67 (2H, s), 7.25-7.36 (8H, m)

SYNTHETIC EXAMPLE 2-2 Synthesis of3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (No. 5-12)

The solution of 1-benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (5.7 g) and 1-chloroethyl chloroformate (4.4 g) indichloroethane was heated to reflux for 3 hours. The mixture was cooledto room temperature and then concentrated under the reduced pressure.Methanol was added to the resultant residue, which was then heated withstirring at 60° C. for two hours. The mixture was cooled to roomtemperature, to which was then added water. The solution was washedtwice with the mixed solvent of hexane and ethyl acetate (9:1). Thesolution was alkalized with sodium hydrogen carbonate and then extractedwith ethyl acetate three times. The organic layer was combined, whichwas then washed with brine and dried over anhydrous magnesium sulfate.After the drying agent was filtered off, the solvent was distilled awayunder the reduced pressure to yield3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (4.2 g). ¹H-NMR(CDCl₃) δ: 2.24-2.33 (1H, m), 2.51-2.56 (1H, m), 2.97-3.07 (1H, m),3.19-3.26 (2H, m), 3.74 (1H, d), 7.25 (2H, d), 7.35 (1H, t)

SYNTHETIC EXAMPLE 2-3 Synthesis of methyl4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoate (No. 4-6)

To the solution of methyl 4-fluoro-2-nitrobenzoate (1.1 g) and3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (1.5 g) in1-methyl-2-pyrrolidinone was added potassium carbonate (1.5 g) and themixture was heated with stirring at 100° C. for two hours. The mixturewas cooled to room temperature and then poured into water, which wasthen extracted twice with ethyl acetate. The organic layer was combined,which was then washed with water and dried over anhydrous magnesiumsulfate. After the drying agent was filtered off, the solvent wasdistilled away under the reduced pressure, and the residue was thenpurified by silica gel chromatography to yield methyl4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoate(1.24 g). ¹H-NMR (CDCl₃) δ: 2.53-2.67 (1H, m), 2.89-2.97 (1H, m),3.50-3.71 (2H, m), 3.83 (1H, d), 3.85 (3H, s), 4.15 (1H, d), 6.69 (1H,dd), 6.75 (1H, d), 7.26 (2H, d), 7.42 (1H, t), 7.81 (1H, d)

SYNTHETIC EXAMPLE 2-4 Synthesis of4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoic acid (No. 4-7)

To the solution of methyl4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoate(1.24 g) in 1,4-dioxane was added 2N aqueous sodium hydroxide (5.4 mL),and the mixture was heated with stirring at 80° C. The mixture wascooled to room temperature and then acidified with 2N hydrochloric acidbefore the mixture was extracted twice with ethyl acetate. The organiclayer was combined, which was then washed with water and dried overanhydrous magnesium sulfate. After the drying agent was filtered off,the solvent was distilled away under the reduced pressure to yield4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoicacid (0.85 g). ¹H-NMR (DMSO-d6) δ: 2.58-2.72 (1H, m), 2.91-3.04 (1H, m),3.47-3.57 (2H, m), 3.87 (1H, d), 4.32 (1H, d), 6.86 (1H, dd), 7.04 (1H,d), 7.65 (2H, d), 7.71 (1H, t), 7.78 (1H, d)

SYNTHETIC EXAMPLE 2-5 Synthesis of4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitro-N-(pyridin-2-ylmethyl)benzamide (No. 1-16)

To the solution of4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitrobenzoicacid (0.3 g) and 2-picolylamine (0.07 g) in DMF was added1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide hydrochloride (0.13 g)and 1-hydroxybenzotriazole monohydrate (0.01 g), and the mixture wasstirred for 6 hour at room temperature. The reaction solution was pouredinto water, which was then extracted twice with ethyl acetate. Theorganic layer was combined, which was then washed with water and driedover anhydrous magnesium sulfate. After the drying agent was filteredoff, the solvent was distilled away under the reduced pressure, and theresidue was then purified by silica gel chromatography to yield4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-nitro-N-(pyridine-2-ylmethyl)benzamide (0.19 g).¹H-NMR (CDCl₃) δ: 2.54-2.65 (1H, m), 2.89-2.97 (1H, m), 3.51-3.67 (2H,m), 3.83 (1H, d), 4.13 (1H, d), 4.74 (2H, d), 6.75 (1H, dd), 7.08 (1H,d), 7.15-7.23 (2H, m), 7.28 (2H, br s), 7.37 (1H, d), 7.41 (1H, t), 7.49(1H, d), 7.70 (1H, td), 8.52 (1H, d).

SYNTHETIC EXAMPLE 32-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-Nyridin-2-ylmethyl)benzenecarbothioamide (No. 1-81)

To the solution of2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin1-yl]-Nyridin-2-ylmethyl)benzamide(0.35 g) in toluene was added Lawesson reagent (0.28 g) and the mixturewas heated to reflux for 3 hours. After the mixture was cooled to roomtemperature, the solvent was distilled away under the reduced pressure,and the residue was purified by silica gel chromatography to yield2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin1-yl]-Nyridin-2-ylmethyl)benzenecarbothioamide(0.10 g). ¹H-NMR (CDCl₃) δ: 2.51-2.61 (11, m), 2.84-2.92 (1H, m),3.45-3.61 (2H, m), 3.79 (1H, d), 4.08 (1H, d), 5.08 (2H, d), 6.49-6.54(2H, m), 7.22-7.28 (3H, m), 7.36 (1H, d), 7.40 (1H, t), 7.72 (1H, td),7.79 (1H, d), 8.54 (1H, d), 9.27 (1H, br s).

SYNTHETIC EXAMPLE 4 Synthesis ofN-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzyl}acetamide (No. 3-3) SYNTHETIC EXAMPLE 4-1Synthesis of 1-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methanamine (No. 4-49)

Sodium tert-butoxide (0.2 g), Tris(dibenzylidene acetone)dipalladium(0)(chloroform adduct)(0.03 g) and xantphos (0.05 g) was added to thesolution of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (0.4g) and 2-(2-chloro-4-iodobenzyl)-1H-isoindole-1,3-(2H)-dione (0.69 g) intoluene under argon atmosphere, and the mixture was heated with stirringat 80° C. for 3 hours. The reaction solution was diluted witht-butylmethylether and then washed with water and brine. The organiclayer was dried over anhydrous magnesium sulfate. The solvent wasdistilled away under the reduced pressure to yield the crude product.The product was dissolved in methanol, to which was then added aqueoushydrazine (0.03 g), followed by the mixture heated to reflux for 12hours. The reaction solution was diluted with t-butylmethylether andthen washed with saturated saline. The organic layer was dried overanhydrous magnesium sulfate. The solvent was distilled away under thereduced pressure, and the residue was then purified by silica gelchromatography to yield1-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methanamine (0.12 g). ¹H-NMR (CDCl₃) δ: 2.47-2.54(1H, m), 2.78-2.85 (1H, m), 3.46-3.49 (2H, m), 3.69-4.01 (4H, m),6.47-6.50 (1H, m), 6.73-6.76 (1H, m), 7.25-7.35 (4H, m).

SYNTHETIC EXAMPLE 4-2 Synthesis ofN-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzyl}acetamide (No. 3-3)

To the solution of1-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}methanamine (0.12 g) and triethylamine (0.04 g)in tetrahydrofuran was added dropwise acetyl chloride (0.02 g), and themixture was stirred for one hour at room temperature. The reactionsolution was diluted with t-butylmethylether and then washed with waterand brine. The organic layer was dried over anhydrous magnesium sulfate.The solvent was distilled away under the reduced pressure, and theresidue was then purified by silica gel chromatography to yieldN-{2-chloro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzyl}acetamide (0.1 g). ¹H-NMR (CDCl₃) δ: 1.98-2.01(3H, m), 2.50-2.58 (1H, m), 2.82-2.87 (1H, m), 3.45-3.51 (2H, m), 3.74(1H, d), 4.02 (1H, d), 4.41 (2H), 6.43-6.46 (1H, m), 6.58-6.59 (1H, m),7.26-7.38 (4H, m)

SYNTHETIC EXAMPLE 5 Synthesis of1-{2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}-1H-tetrazole (No. 2-23) SYNTHETIC EXAMPLE 5-1Synthesis of1-(bromo-4-nitrophenyl)-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine(No. 4-20)

To the solution of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine(1.3 g) and 2-bromo-4-fluoro-1-nitrobenzene (1.0 g) in1-methyl-2-pyrrolidinone was added potassium carbonate (1.3 g), and themixture was heated with stirring at 100° C. for 3 hours. The mixture wascooled to room temperature and then poured into water, which wasextracted twice with ethyl acetate. The organic layer was combined,which was then washed with water and dried over anhydrous magnesiumsulfate. After the drying agent was filtered off, the solvent wasdistilled away under the reduced pressure, and the residue was thenpurified by silica gel chromatography to yield1-(3-bromo-4-nitrophenyl)-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine(1.56 g). ¹H-NMR (CDCl₃) δ: 2.53-2.66 (1H, m), 2.89-2.97 (1H, m),3.51-3.71 (2H, m), 3.83 (1H, d), 4.16 (1H, d), 6.53 (1H, dd), 6.84 (1H,d), 7.27 (2H, br s), 7.42 (1H, t), 8.07 (1H, d).

SYNTHETIC EXAMPLE 5-2 Synthesis of2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-pyrrolidin-1-yl]aniline(No. 4-21)

To the solution of1-(3-bromo-4-nitrophenyl)-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine(1.10 g) in the mixed solvent of 1,4-dioxane and ethanol was addedstannous chloride dihydrate (2.05 g) and a small amount of concentratedhydrochloric acid, and the mixture was then stirred 4 hours at 90° C.The mixture was cooled to room temperature and then poured into themixed solution of ethyl acetate and water, which was then neutralizedwith sodium hydrogen carbonate with vigorous stirring. After filtrationof precipitate through Celite, the organic layer was separated and theaqueous layer was extracted with ethyl acetate. The organic layer wascombined, which was then washed with brine and dried over anhydrousmagnesium sulfate. After the drying agent was filtered off, the solventwas distilled away under the reduced pressure, and the residue was thenpurified by silica gel chromatography to yield2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-pyrrolidin-1-yl]aniline(0.73 g). ¹H-NMR (CDCl₃) δ: 2.44-2.54 (1H, m), 2.75-2.83 (1H, m),3.32-3.50 (2H, m), 3.56-3.76 (3H, m), 3.92 (1H, d), 6.46 (1H, dd),6.70-6.78 (2H, m), 7.29 (2H, br s), 7.37 (1H, t).

SYNTHETIC EXAMPLE 5-3 Synthesis of1-{2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl}-1H-tetrazole(No. 2-23)

To the mixture of2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-pyrrolidin-1-yl]aniline(0.60 g), triethyl orthoformate (0.98 g) and sodium azide (0.38 g) wasadded acetic acid (1.1 g), and the mixture was then heated with stirringat 100° C. for 4 hours. The mixture was cooled to room temperature andthen poured into water, which was then extracted twice with ethylacetate. The organic layer was combined, which was then washed withwater and dried over anhydrous magnesium sulfate. After the drying agentwas filtered off, the solvent was distilled away under the reducedpressure, and the residue was then purified by silica gel chromatographyto yield1-{2-bromo-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-pyrrolidin-1-yl]phenyl}-1H-tetrazole(0.52 g). m.p. 193-194° C.

SYNTHETIC EXAMPLE 6 Synthesis of5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (No. 2-39)SYNTHETIC EXAMPLE 6-1 Synthesis of5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-fluorobenzonitrile (No. 4-17)

3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (0.6 g) and2-fluoro-5-iodobenzonitrile (0.57 g) was dissolved in toluene, which wasthen degassed 3 times. To the solution in toluene was added sodiumtert-butoxide (0.20 g), Tris(dibenzylidene acetone)dipalladiumchloroform complex (0.04 g) and Xantphos (0.07 g) under argonatmosphere, and the mixture was stirred at 80° C. for two hours. Themixture was cooled to room temperature and then diluted with ethylacetate, which was then washed with water and dried over anhydrousmagnesium sulfate. After the drying agent was filtered off, the solventwas distilled away under the reduced pressure, and the residue was thenpurified by silica gel chromatography to yield5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-fluorobenzonitrile(0.54 g). m.p. 184-186° C.

SYNTHETIC EXAMPLE 6-2 Synthesis of5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (No. 2-39)

To the solution of 1H-1,2,4-triazole (0.06 g) in DMF was added sodiumhydride (0.04 g) while cooling with ice, and the mixture was warmed toroom temperature and then stirred for 0.5 hr. To this solution was addedthe solution of 5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]2-fluorobenzonitrile (0.30 g) in DMF, and the mixturewas heated to reflux for 6 hours. The mixture was cooled to roomtemperature and then poured into water, which was then extracted twicewith ethyl acetate. The organic layer was combined, which was thenwashed with water and dried over anhydrous magnesium sulfate. After thedrying agent was filtered off, the solvent was distilled away under thereduced pressure, and the residue was then purified by silica gelchromatography to yield 5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (0.18 g). ¹H-NMR(DMSO-d6) δ: 2.62-2.73 (1H, m), 2.95-3.03 (1H, m), 3.49-3.55 (2H, m),3.90 (1H, d), 4.31 (1H, d), 7.09 (1H, dd), 7.29 (1H, d), 7.61 (1H, d),7.68 (2H, d), 7.71 (111H, t), 8.26 (1H, s), 8.98 (1H, s)

SYNTHETIC EXAMPLE 7 Synthesis of1,3-dimethyl-2-nitro-5-[1-(trifluoromethyl) vinyl]benzene (No. 6-1)

5-bromo-1,3-dimethyl-2-nitrobenzene (10.0 g), [1-(trifluoromethyl)vinyl]boronic acid (purity: 60%, 13.4 g) and potassium carbonate (14.4g) was dissolved in the mixed solvent of THF and water, which was thendegassed three times. To the solution was added dichlorobis(triphenylphosphine) palladium (II) (1.5 g), and the mixture washeated to reflux for 3 hours under argon atmosphere. The mixture wascooled to room temperature and then poured into water, which was thenextracted twice with ethyl acetate. The organic layer was combined,which was then washed with water and dried over anhydrous magnesiumsulfate. After the drying agent was filtered off, the solvent wasdistilled away under the reduced pressure, and the residue was thenpurified by silica gel chromatography to yield1,3-dimethyl-2-nitro-5-[l-(trifluoromethyl) vinyl]benzene (11.2 g).¹H-NMR (CDCl₃) δ: 2.34 (6H, s), 5.78-5.80 (1H, m), 6.03-6.04 (1H, m),7.20 (2H, s).

SYNTHETIC EXAMPLE 8 Synthesis of4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzonitrile (No. 4-2)

To the solution of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (0.30 g) and 4-fluorobenzonitrile (0.12 g) in DMSO(dimethylsurufoxide) was added potassium carbonate (0.27 g), and themixture was heated with stirring at 120° C. for 6 hours. The mixture wascooled to room temperature and then poured onto water, which was thenextracted twice with ethyl acetate. The organic layer was combined,which was then washed with water and dried over anhydrous magnesiumsulfate. After the drying agent was filtered off, the solvent wasdistilled away under the reduced pressure, and the residue was thenpurified by silica gel chromatography to yield4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]benzonitrile (0.05 g). ¹H-NMR (CDCl₃) δ: 2.51-2.62 (1H,m), 2.86-2.94 (1H, m), 3.56-3.61 (2H, m), 3.80 (1H, d), 4.12 (1H, d),6.59 (2H, d), 7.26 (2H, br s), 7.41 (1H, t), 7.52 (2H, d).

The compounds and intermediates of the formula (I) or formula (Ia) ofthe invention obtained by the same methods as those of the abovesynthetic examples and according to the methods described above indetail, as well as their physical values are showed in tables 1-13. Eachcompound obtained in the above synthetic examples is also showed in eachcorrespondent table.

In these tables, the following abbreviations are used.

Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, Ph: phenyl, Pen: pentyl.

TABLE 1

(X)m R Y R1 R2 A W m. p. °(C.) 1-1 3,5-diCl CF3 H CF3CH2 H CH O 1-23,5-diCl CF3 H 2-PyridylCH2 H CH O 1-3 3,5-diCl CF3 CH3 CF3CH2 H CH O1-4 3,5-diCl CF3 CH3 2-PyridylCH2 H CH O 1-5 3,5-diCl CF3 F CF3CH2 H CHO 1-6 3,5-diCl CF3 F 2-PyridylCH2 H CH O 1-7 3,5-diCl CF3 Cl CF3CH2 H CHO 1-8 3,5-diCl CF3 Cl 2-PyridylCH2 H CH O 1-9 3,5-diCl CF3 Br CF3CH2 HCH O 1-10 3,5-diCl CF3 Br 2-PyridylCH2 H CH O 1-11 3,5-diCl CF3 Brcyclo-Pr H CH O 1-12 3,5-diCl CF3 Br NCCH2CH2 H CH O 1-13 3,5-diCl CF3 ICF3CH2 H CH O 1-14 3,5-diCl CF3 I 2-PyridylCH2 H CH O 1-15 3,5-diCl CF3NO2 CF3CH2 H CH O 1-16 3,5-diCl CF3 NO2 2-PyridylCH2 H CH O 1-17 3-ClCF3 NO2 2-PyridylCH2 H CH O 1-18 3-Cl CF3 NO2 CF3CH2 H CH O 1-19 3-BrCF3 NO2 2-PyridylCH2 H CH O 1-20 3-CF3 CF3 NO2 2-PyridylCH2 H CH O169-170 1-21 3-CF3 CF3 NO2 CF3CH2 H CH O 1-22 3,5-diCF3 CF3 NO22-PyridylCH2 H CH O 1-23 3,5-diCF3 CF3 NO2 CF3CH2 H CH O 1-24 3-NO2 CF3NO2 2-PyridylCH2 H CH O 176-179 1-25 3,5-diCl CF3 CF3 2-PyridylCH2 H CHO 1-26 3,5-diCl CF3 CH3O 2-PyridylCH2 H CH O 1-27 3,5-diCl CF3 CN2-PyridylCH2 H CH O 1-28 3,5-diCl CF3 CF3O 2-PyridylCH2 H CH O 1-293,5-diCl CF3 CH3S 2-PyridylCH2 H CH O 1-30 3,5-diCl CF3 CH3S(O)2-PyfidylCH2 H CH O 1-31 3,5-diCl CF3 CH3S(O)2 2-PyridylCH2 H CH O 1-323,5-diCl CF3 CF3S 2-PyridylCH2 H CH O 1-33 3,5-diCl CF3 CF3S(O)2-PyridylCH2 H CH O 1-34 3,5-diCl CF3 CF3S(O)2 2-PyridylCH2 H CH O 1-353,5-diCl CF3 OH 2-PyridylCH2 H CH O 1-36 3,5-diCl CF3 SH 2-PyridylCH2 HCH O 1-37 3,5-diCl CF3 NH2 2-PyridylCH2 H CH O 1-38 3,5-diCl CF3 NHCOCH32-PyridylCH2 H CH O 1-39 3,5-diCl CF3 NHCOCF3 2-PyridylCH2 H CH O 1-403,5-diCl CF3 NHCO2CH3 2-PyridylCH2 H CH O 1-41 3,5-diCl CF3 NHCO2CH2CCl32-PyridylCH2 H CH O 1-42 3-CH3 CF3 H 2-PyridylCH2 H CH O 1-43 3-CH3O CF3H 2-PyridylCH2 H CH O 1-44 3-CN CF3 H 2-PyridylCH2 H CH O 1-45 3-CF3OCF3 H 2-PyridylCH2 H CH O 1-46 3-CH3S CF3 H 2-PyridylCH2 H CH O 1-473-CH3S(O) CF3 H 2-PyridylCH2 H CH O 1-48 3-CH3S(O)2 CF3 H 2-PyridylCH2 HCH O 1-49 3-CF3S CF3 H 2-PyridylCH2 H CH O 1-50 3-CF3S(O) CF3 H2-PyridylCH2 H CH O 1-51 3-CF3S(O)2 CF3 H 2-PyridylCH2 H CH O 1-52 3-OHCF3 H 2-PyridylCH2 H CH O 1-53 3-SH CF3 H 2-PyridylCH2 H CH O 1-543,4-diCl CF3 H 2-PyridylCH2 H CH O 1-55 3,4-diCl CF3 H CF3CH2 H CH O77-80 1-56 3,4,5-triCl CF3 H 2-PyridylCH2 H CH O 1-57 3,4,5-triCl CF3 HCF3CH2 H CH O 1-58 3,5-diBr CF3 H 2-PyridylCH2 H CH O 1-59 3,5-diBr CF3H CF3CH2 H CH O 1-60 3,5-diMe-4-NO2 CF3 H 2-PyridylCH2 H CH O 1-613,5-diMe-4-NO2 CF3 H CF3CH2 H CH O 1-62 3,5-diCl CF3 H 2-PyridylCH2 H CHS 1-63 3,5-diCl CF3 NO2 H H CH O 1-64 3,5-diCl CF3 NO2 Me H CH O 1-653,5-diCl CF3 NO2 iso-Pr H CH O 1-66 3,5-diCl CF3 NO2 PhCH2 H CH O 1-673,5-diCl CF3 NO2 CH2CO2CH3 H CH O 1-68 3,5-diCl CF3 NO2 CH2CONMe H CH O1-69 3,5-diCl CF3 NO2 CH2(cyclo)Pr H CH O 1-70 3,5-diCl CF3 NO2 SO2Me HCH O 1-71 3,5-diCl CF3 NO2 SO2CF3 H CH O 1-72 3,5-diCl CF3 NO2 CH2═CHCH2H CH O 1-73 3,5-diCl CF3 NO2 HCCCH2 H CH O 1-74 3,5-diCl CF3 NO2 CH2CN HCH O 1-75 3,5-diCl CF3 NO2 C(Me)2CH2SCH3 H CH O 1-76 3,5-diCl CF3 NO22-F-Ph H CH O 1-77 3,5-diCl CH3 H 2-PyridylCH2 H CH O 1-78 3,5-diCl CF3H 2-PyridylCH2 H N O 1-79 3,5-diCl CF3 H 2-PyridylCH2 CH3 CH O 1-803-NO2 CF3 NO2 CF3CH2 H CH O 1-81 3,5-diCl CF3 Cl 2-PyridylCH2 H CH S1-82 2-diCl CF3 NO2 2-PyridylCH2 H CH O 1-83 2,3-diCl CF3 NO22-PyridylCH2 H CH O 1-84 3,5-diCl CF3 NO2 3-PyridylCH2 H CH O 1-853,5-diCl CF3 NO2 4-PyridylCH2 H CH O 1-86 3,5-diCl CF3 NO22-(6-Cl-pyridyl)CH2 H CH O 1-87 3,5-diCl CF3 NO2 3-(6-Cl-pyridyl)CH2 HCH O 1-88 3,5-diCl CF3 NO2 2-PyrinidinylCH2 H CH O 1-89 3,5-diCl CF3 NO21-(1-ethylpyrrolidin- H CH O 2-y1)CH2 1-90 3,5-diCl CF3 CF3 CF3CH2 H CHO 1-91 3,5-diCl CF3 CF3 2-(6-Cl-pyridyl)CH2 H CH O 1-92 3,5-diCl CF3 NO2Me2NCH═ CH O 1-93 3,5-diCl CF3 NO2 EtON═CH H CH O 1-94 3,5-diCl CF3C═NOCH3 2-PyridylCH2 H CH O 1-95 4-Cl CF3 NO2 2-PyridylCH2 H CH O 1-964-Cl CF3 NO2 CF3CH2 H CH O 1-97 3,5-diCl CF3 CN CF3CH2 H CH O 1-983,5-diCl CF3 CF3 H H CH O 1-99 3,5-diCF3 CF3 CF3 2-PyridylCH2 H CH O1-100 3,5-diCF3 CF3 CF3 CF3CH2 H CH O 1-101 3,5-diCl CF3 H CF3CH2 H N O1-102 3,4,5-triCl CF3 CF3 2-PyridylCH2 H CH O

TABLE 2

(X)m R Y G Z A m.p. °(C.) 2-1 3,5-diCl CF3 H G1 H CH 2-2 3,5-diCl CF3 HG2 H CH 2-3 3,5-diCl CF3 H G3 H CH 2-4 3,5-diCl CF3 H G4 H CH 2-53,5-diCl CF3 H G5 H CH 2-6 3,5-diCl CF3 H G6 H CH 2-7 3,5-diCl CF3 H G7H CH 2-8 3,5-diCl CF3 H G8 H CH 2-9 3,5-diCl CF3 H G9 H CH 2-10 3,5-diClCF3 F G6 H CH 2-11 3,5-diCl CF3 F G8 H CH 2-12 3,5-diCl CF3 F G9 H CH2-13 3,5-diCl CF3 Cl G6 H CH 2-14 3,5-diCl CF3 Cl G8 H CH 2-15 3,5-diClCF3 Cl G9 H CH 2-16 3,5-diCl CF3 Br G1 H CH 2-17 3,5-diCl CF3 Br G2 H CH2-18 3,5-diCl CF3 Br G3 H CH 2-19 3,5-diCl CF3 Br G4 H CH 2-20 3,5-diClCF3 Br G5 H CH 2-21 3,5-diCl CF3 Br G6 H CH 2-22 3,5-diCl CF3 Br G7 H CH2-23 3,5-diCl CF3 Br G8 H CH 193-194 2-24 3,5-diCl CF3 Br G9 H CH 2-253,5-diCl CF3 I G6 H CH 2-26 3,5-diCl CF3 I G8 H CH 2-27 3,5-diCl CF3 IG9 H CH 2-28 3,5-diCl CF3 Me G6 H CH 2-29 3,5-diCl CF3 Me G8 H CH 2-303,5-diCl CF3 CF3 G6 H CH 2-31 3,5-diCl CF3 CF3 G8 H CH 2-32 3,5-diCl CF3NO2 G6 H CH 2-33 3,5-diCl CF3 NO2 G8 H CH 2-34 3,5-diCl CF3 CN G1 H CH2-35 3,5-diCl CF3 CN G2 H CH 2-36 3,5-diCl CF3 CN G3 H CH 2-37 3,5-diClCF3 CN G4 H CH 2-38 3,5-diCl CF3 CN G5 H CH 2-39 3,5-diCl CF3 CN G6 H CH2-40 3,5-diCl CF3 CN G7 H CH 2-41 3,5-diCl CF3 CN G8 H CH 192-193 2-423,5-diCl CF3 CN G9 H CH 2-43 3,5-diCl CF3 NO2 G6 H CH 2-44 3,5-diCl CF3NO2 G8 H CH 2-45 3,5-diCl CF3 CH3 G6 H CH 2-46 3,5-diCl CF3 MeS G6 H CH2-47 3,5-diCl CF3 MeSO G6 H CH 2-48 3,5-diCl CF3 MeSO2 G6 H CH 2-493,5-diCl CF3 CF3S G6 H CH 2-50 3,5-diCl CF3 CF3S(O) G6 H CH 2-513,5-diCl CF3 CF3S(O)2 G6 H CH 2-52 3,5-diCl CF3 OCH3 G6 H CH 2-533,5-diCl CF3 OCF3 G6 H CH 2-54 3,5-diCl CF3 OH G6 H CH 2-55 3,5-diCl CF3SH G6 H CH 2-56 3,5-diCl CF3 NH2 G6 H CH 2-57 3,5-diCl CF3 NHCOCH3 G6 HCH 2-58 3,5-diCl CF3 NHCO2CH3 G6 H CH 2-59 3,5-diCl CF3 NHCO2CH2 G6 H CHCCl3 2-60 3,5-diCl CF3 CN G2 3-NO2 CH 2-61 3,5-diCl CF3 CN G2 3-CN CH2-62 3,5-diCl CF3 CN G6 3-NO2 CH 2-63 3,5-diCl CF3 CN G6 3-CN CH 2-643,5-diCl CF3 CN G2 Cl CH 2-65 3,5-diCl CF3 CN G2 Br CH 2-66 3,5-diCl CF3CN G2 CH3 CH 2-67 3,5-diCl CF3 CN G2 CF3 CH 2-68 3-Cl CF3 CN G6 H CH2-69 3-Cl CF3 CN G8 H CH 2-70 3-CF3 CF3 CN G6 H CH 2-71 3-CF3 CF3 CN G8H CH 2-72 3,5-diCF3 CF3 CN G6 H CH 2-73 3,5-diCF3 CF3 CN G8 H CH 2-743-NO2 CF3 CN G6 H CH 2-75 3-NO2 CF3 CN G8 H CH 2-76 3,4-diCl CF3 CN G6 HCH 2-77 3,4-diCl CF3 CN G8 H CH 2-78 3,5-diBr CF3 CN G6 H CH 2-793,5-diBr CF3 CN G8 H CH 2-80 3,5-diBr CF3 Br G6 H CH 2-81 3,5-diBr CF3Br G8 H CH 2-82 3,4,5-triCl CF3 CN G6 H CH 2-83 3,4,5-triCl CF3 CN G8 HCH 2-84 3,4,5-triCl CF3 Br G6 H CH 2-85 3,4,5-triCl CF3 Br G8 H CH 2-863,5-diMe- CF3 CN G8 H CH 4-NO2 2-87 3-CH3 CF3 CN G6 H CH 2-88 3-CH3O CF3CN G6 H CH 2-89 3-CN CF3 CN G6 H CH 2-90 3-CF3O CF3 CN G6 H CH 2-913-CF3O CF3 CN G8 H CH 2-92 3-CH3S CF3 CN G6 H CH 2-93 3-CH3S CF3 CN G8 HCH 2-94 3-CH3S(O) CF3 CN G6 H CH 2-95 3-CH3S(O)2 CF3 CN G6 H CH 2-963-CF3S CF3 CN G6 H CH 2-97 3-CF3S(O) CF3 CN G6 H CH 2-98 3-CF3S(O)2 CF3CN G6 H CH 2-99 3-OH CF3 CN G6 H CH 2-100 3-SH CF3 CN G6 H CH 2-1013,5-diCl CH3 Br G6 H CH 2-102 3,5-diCl CH3 Br G8 H CH 2-103 3,5-diCl CF3Br G6 H N 2-104 3,5-diCl CF3 Br G8 H N 2-105 3,5-diCl CF3 CN G6 H N2-106 3,5-diCl CF3 CN G8 H N 2-107 3,5-diCl CF3 C═NOCH3 G6 H CH 2-1083,5-diCl CF3 C═NOCH3 G8 H CH 2-109 3,5-diCl CF3 NHSO2CH3 G6 H CH 2-1103,5-diCl CF3 NHSO2CH3 G8 H CH 2-111 3,5-diCl CF3 NHSO2CF3 G6 H CH 2-1123,5-diCl CF3 NHSO2CF3 G8 H CH

TABLE 3

(X)m R Y R2 R3 R4 R5 A I m.p. °(C.) 3-1 3,5-diCl CF3 H H H H COCH3 CH 13-2 3,5-diCl CF3 H H H H COC2H5 CH 1 3-3 3,5-diCl CF3 Cl H H H COCH3 CH1 3-4 3,5-diCl CF3 Br H H H COCH3 CH 1 3-5 3,5-diCl CF3 Br H H H COC2H5CH 1 3-6 3,5-diCl CF3 Br H H H CO(i-Pr) CH 1 3-7 3,5-diCl CF3 Br H H HCO2-pyridyl CH 1 3-8 3,5-diCl CF3 F H H H COCH3 CH 1 3-9 3,5-diCl CF3 IH H H COCH3 CH 1 3-10 3,5-diCl CF3 NO2 H H H COCH3 CH 1 3-11 3,5-diClCF3 CH3 H H H COCH3 CH 1 3-12 3,5-diCl CF3 MeS H H H COCH3 CH 1 3-133,5-diCl CF3 MeSO H H H COCH3 CH 1 3-14 3 5-diCl CF3 MeSO2 H H H COCH3CH 1 3-15 3,5-diCl CF3 CF3S H H H COCH3 CH 1 3-16 3,5-diCl CF3 CF3S(O) HH H COCH3 CH 1 3-17 3 5-diCl CF3 CF3S(O)2 H H H COCH3 CH 1 3-18 3,5-diClCF3 OCH3 H H H COCH3 CH 1 3-19 3,5-diCl CF3 OCF3 H H H COCH3 CH 1 3-203,5-diCl CF3 OH H H H COCH3 CH 1 3-21 3,5-diCl CF3 SH H H H COCH3 CH 13-22 3,5-diCl CF3 NH2 H H H COCH3 CH 1 3-23 3,5-diCl CF3 NHCOCH3 H H HCOCH3 CH 1 3-24 3 5-diCl CF3 NHCO2CH3 H H H COCH3 CH 1 3-25 3,5-diCl CF3NHCO2CH2CCl3 H H H COCH3 CH 1 3-26 3 5-diCl CF3 Cl H H Me CO2-pyridyl CH1 3-27 3,5-diCl CF3 Cl H H Me COCH3 CH 1 3-28 3,5-diCl CF3 Cl H H EtCOCH3 CH 1 3-29 3,5-diCl CF3 Cl H H vinyl COCH3 CH 1 3-30 3 5-diCl CF3Cl H H propargyl COCH3 CH 1 3-31 3,5-diCl CF3 Cl H H CH2Ph COCH3 CH 13-32 3,5-diCl CF3 Cl H H CN COCH3 CH 1 3-33 3 5-diCl CF3 Cl H H CH2CF3COCH3 CH 1 3-34 3,5-diCl CF3 Cl H H cycloPr COCH3 CH 1 3-35 3,5-diCl CF3Cl H H COCH3 COCH3 CH 1 3-36 3,5-diCl CF3 Cl H H H COC2H5 CH 1 3-373,5-diCl CF3 Cl H H H COC2F5 CH 1 3-38 3,5-diCl CF3 Cl H H H COPh CH 13-39 3,5-diCl CF3 Cl H H H CO2-pyridyl CH 1 3-40 3 5-diCl CF3 Cl H H HCONMe2 CH 1 3-41 3,5-diCl CF3 Cl H H H CO2Me CH 1 3-42 3,5-diCl CF3 Cl HH H COSMe CH 1 3-43 3 5-diCl CF3 Cl H H Me COCH3 CH 1 3-44 3,5-diCl CF3Cl H H 2-pyridylCO COCH3 CH 1 3-45 3,5-diBr CF3 Cl H H H COCH3 CH 1 3-463-Cl CF3 Cl H H H COCH3 CH 1 3-47 3-CF3 CF3 Cl H H H COCH3 CH 1 3-483,5-diCF3 CF3 Cl H H H COCH3 CH 1 3-49 3,4,5-triCl CF3 Cl H H H COCH3 CH1 3-50 3,5-diMe-4-NO2 CF3 Cl H H H COCH3 CH 1 3-51 3-NO2 CF3 Cl H H HCOCH3 CH 1 3-52 3,5-diCl CF3 Cl H H H COCH3 N 1 3-53 3-CH3 CF3 Cl H H HCOCH3 CH 1 3-54 3-CH3O CF3 Cl H H H COCH3 CH 1 3-55 3-CN CF3 Cl H H HCOCH3 CH 1 3-56 3-CF3O CF3 Cl H H H COCH3 CH 1 3-57 3-CH3S CF3 Cl H H HCOCH3 CH 1 3-58 3-CH3S(O) CF3 Cl H H H COCH3 CH 1 3-59 3-CH3S(O)2 CF3 ClH H H COCH3 CH 1 3-60 3-CF3S CF3 Cl H H H COCH3 CH 1 3-61 3-CF3S(O) CF3Cl H H H COCH3 CH 1 3-62 3-CF3S(O)2 CF3 Cl H H H COCH3 CH 1 3-63 3-OHCF3 Cl H H H COCH3 CH 1 3-64 3-SH CF3 Cl H H H COCH3 CH 1 3-65 3,5-diClCF3 Cl CN H H COCH3 CH 1 3-66 3,5-diCl CF3 Cl Me H H COCH3 CH 1 3-673,5-diCl CF3 Cl Me Me H COCH3 CH 1 3-68 3,5-diCl CF3 Cl cyclo-Pr H HCOCH3 CH 1 3-69 3,5-diCl CF3 Cl CF3 H H COCH3 CH 1 3-70 3,5-diCl CF3 ClCO2Me H H COCH3 CH 1 3-71 3,5-diCl CF3 Cl CH═CH2 H H COCH3 CH 1 3-723,5-diCl CF3 Cl CH2CH2 H COCH3 CH 1 3-73 3,5-diCl CF3 Cl CCH H H COCH3CH 1 3-74 3,5-diCl CF3 Br H H H COEt CH 1 3-75 3,5-diCl CF3 Br H H HCOPr-n CH 1 3-76 3,5-diCl CF3 Br H H H COPr-iso CH 1 3-77 3,5-diCl CF3Br H H H COBu-tert CH 1 3-78 3,5-diCl CF3 Br H H H COCF3 CH 1 3-793,5-diCl CF3 Br H H H COPh CH 1 3-80 3,5-diCl CF3 Br H H H COpyridyl-2CH 1 3-81 3,5-diCl CF3 Br H H H COpyridyl-3 CH 1 3-82 3,5-diCl CF3 Br HH H COpyridylCO-4 CH 1 3-83 3,5-diCl CF3 Br H H H COPh-F-2 CH 1 3-843,5-diCl CF3 Br H H H COPh-F-3 CH 1 3-85 3,5-diCl CF3 Br H H H COPh-F-4CH 1 3-86 3,5-diCl CF3 Br H H H COPh-Cl-2 CH 1 3-87 3,5-diCl CF3 Br H HH COPh-Cl-3 CH 1 3-88 3,5-diCl CF3 Br H H H COPh-Cl-4 CH 1 3-89 3,5-diClCF3 Br H H H COPh-Br-2 CH 1 3-90 3,5-diCl CF3 Br H H H COPh-Me-2 CH 13-91 3,5-diCl CF3 Br H H H Covinyl CH 1 3-92 3,5-diCl CF3 Br H H HCOpropargyl CH 1 3-93 3,5-diCl CF3 Br H H H MeSO2 CH 1 3-94 3,5-diCl CF3Br H H H CF3SO2 CH 1 3-95 3,5-diCl CF3 Br H H H CONHMe CH 1 3-963,5-diCl CF3 Br H H H CONMe2 CH 1 3-97 3,5-diCl CF3 Br H H H CO2Me CH 13-98 3,5-diCl CF3 Br H H H C(O)SMe CH 1 3-99 3,5-diCl CF3 Br H H H CSMeCH 1 3-100 3,5-diCl CF3 Br H H H CON(Me)OMe CH 1 3-101 3,5-diCl CH3 Br HH H COCH3 CH 1 3-102 3,5-diCl CH3 CF3 H H H COCH3 CH 1 3-103 3,5-dIClCH3 CN H H H COCH3 CH 1 3-104 3,5-diCl CH3 NH2 H H H COCH3 CH 1 3-1053,5-diCl CH3 NHCOCH3 H H H COCH3 CH 1 3-106 3,5-diCl CH3 NHCOCF3 H H HCOCH3 CH 1 3-107 3,5-diCl CH3 NHCO2CH3 H H H COCH3 CH 1 3-108 3,5-diClCH3 NHCO2CH2CCl3 H H H COCH3 CH 1 3-109 3,5-diCl CH3 NHSO2CH3 H H HCOCH3 CH 1 3-110 3,5-diCl CH3 NHSO2CF3 H H H COCH3 CH 1 3-111 3,5-diClCH3 C═NOCH3 H H H COCH3 CH 1 3-112 3,5-diCl CF3 Br H H H COCH3 CH 23-113 3,5-diCF3 CF3 CF3 H H H COCH3 CH 1 3-114 3,5-diCF3 CF3 CF3 H H HCOC2H5 CH 1 3-115 3,5-diCF3 CF3 CF3 H H H COPr-cyclo CH 1 3-1163,4,5-triCl CF3 CF3 H H H COCH3 CH 1 3-117 3,4,5-triCl CF3 CF3 H H HCOC2H5 CH 1 3-118 3,4,5-triCl CF3 CF3 H H H COPr-cyclo CH 1 3-1193,4-diCl, 5-CF3 CF3 CF3 H H H COCH3 CH 1

TABLE 4

(X)m R Y T⁴ A m.p. °(C.) 4-1 3,5-diCl CF3 H NO2 CH 4-2 3,5-diCl CF3 H CNCH 4-3 3,5-diCl CF3 H NH2 CH 4-4 3,5-diCl CF3 H CO2Et CH 161-163 4-53,5-diCl CF3 H CO2H CH 4-6 3,5-diCl CF3 NO2 CO2Me CH 4-7 3,5-diCl CF3NO2 CO2H CH 4-8 3,5-diCl CF3 NH2 CO2Me CH 4-9 3,5-diCl CF3 F CO2Me CH4-10 3,5-diCl CF3 Cl CO2Me CH 4-11 3,5-diCl CF3 Cl CO2Bu-t CH 4-123,5-diCl CF3 Cl CO2H CH 4-13 3,5-diCl CF3 Br CO2Me CH 4-14 3,5-diCl CF3I CO2Me CH 4-15 3,5-diCl CF3 CH3 CO2Me CH 4-16 3,5-diCl CF3 Cl CH3 CH4-17 3,5-diCl CF3 CN F CH 184-186 4-18 3,5-diCl CF3 CH3 NO2 CH 4-193,5-diCl CF3 CH3 NH2 CH 4-20 3,5-diCl CF3 Br NO2 CH 4-21 3,5-diCl CF3 BrNH2 CH 4-22 3-CF3 CF3 NO2 CO2Me CH 146-148 4-23 3-CF3 CF3 NO2 CO2H CH4-24 3,5-diCF3 CF3 NO2 CO2Me CH 4-25 3,5-diCF3 CF3 NO2 CO2H CH 4-263,4-diCl CF3 NO2 CO2Me CH 4-27 3,4-diCl CF3 NO2 CO2H CH 4-28 3-Cl CF3NO2 CO2Me CH 142-144 4-29 3-Cl CF3 NO2 CO2H CH 4-30 3,5-diBr CF3 NO2CO2Me CH 4-31 3,4,5-triCl CF3 NO2 CO2Me CH 4-32 3,5-diMe-4-NO2 CF3 NO2CO2Me CH 4-33 3-NO2 CF3 NO2 CO2Me CH 4-34 3-CH3 CF3 NO2 CO2Me CH 4-353-CH3O CF3 NO2 CO2Me CH 4-36 3-CN CF3 NO2 CO2Me CH 4-37 3-CF3O CF3 NO2CO2Me CH 4-38 3-CH3S CF3 NO2 CO2Me CH 4-39 3-CH3S(O) CF3 NO2 CO2Me CH4-40 3-CH3S(O)2 CF3 NO2 CO2Me CH 4-41 3-CF3S CF3 NO2 CO2Me CH 4-423-CF3S(O) CF3 NO2 CO2Me CH 4-43 3-CF3S(O)2 CF3 NO2 CO2Me CH 4-44 3-OHCF3 NO2 CO2Me CH 4-45 3-SH CF3 NO2 CO2Me CH 4-46 3,5-diCl CF3 H CO2Me N4-47 3-NO2 CF3 NO2 CO2H CH 4-48 3,4,5-triCl CF3 NO2 CO2H CH 4-49 2-ClCF3 NO2 CO2Me CH 4-50 2-Cl CF3 NO2 CO2H CH 4-51 4-Cl CF3 NO2 CO2Me CH4-52 4-Cl CF3 NO2 CO2H CH 4-53 3,5-diCl CF3 CF3 CO2Et CH 4-54 3,5-diClCF3 CF3 CO2H CH 4-55 3,5-diMe-4-NO2 CF3 NO2 CO2H CH 4-56 3,4,5-triCl CF3NO2 CO2Me CH 4-57 3,5-diCl CF3 CN CO2H CH 4-58 3,5-diCl CF3 CN CO2Me CH4-59 3,5-diCl CF3 H CO2Bu-t N 4-60 3,5-diCl CF3 H CO2H N 4-61 3,5-diCF3CF3 CF3 CO2Et CH 4-62 3,5-diCl CF3 CF3 F CH 4-63 3,5-diCl CF3 CF3 NO2 CH4-64 3,5-diCl CF3 CF3 NH2 CH 4-65 3,5-diCl CF3 F CO2Et CH 4-663,4,5-triCl CF3 CF3 CO2Et CH 4-67 3,4,5-triCl CF3 CF3 CO2H CH

TABLE 5

(X)m R T¹ m.p. °(C.) 5-1 2-Cl CF3 CH₂Ph 5-2 2-Cl CF3 H 5-3 3-Cl CF3CH₂Ph 5-4 3-Cl CF3 H 5-5 4-Cl CF3 CH₂Ph 5-6 4-Cl CF3 H 5-7 2,3-diCl CF3CH₂Ph 5-8 2,3-diCl CF3 H 5-9 3,4-diCl CF3 CH₂Ph 5-10 3,4-diCl CF3 H 5-113,5-diCl CF3 CH₂Ph 5-12 3,5-diCl CF3 H 5-13 3,5-diCl CF3 H, HCl salt5-14 3,4,5-triCl CF3 CH₂Ph 5-15 3,4,5-triCl CF3 H 5-16 3-CF3 CF3 CH₂Ph5-17 3-CF3 CF3 H 5-18 3,5-diCF3 CF3 CH₂Ph 5-19 3,5-diCF3 CF3 H 5-20 3-BrCF3 CH₂Ph 5-21 3-Br CF3 H 5-22 3,5-diBr CF3 CH₂Ph 5-23 3,5-diBr CF3 H5-24 3-NO2 CF3 CH₂Ph 5-25 3-NO2 CF3 H 5-26 3,5-diMe-4-NO2 CF3 CH₂Ph 5-273,5-diMe-4-NO2 CF3 H 5-28 3-CN CF3 CH₂Ph 5-29 3-CN CF3 H 5-30 3-OCF₃ CF3CH₂Ph 5-31 3-OCF₃ CF3 H 5-32 3-SCF₃ CF3 CH₂Ph 5-33 3-SCF₃ CF3 H 5-343-S(O)CF₃ CF3 CH₂Ph 5-35 3-S(O)CF₃ CF3 H 5-36 3-S(O)₂CF₃ CF3 CH₂Ph 5-373-S(O)₂C F₃ CF3 H 5-38 3,4-diCl, 5-CF3 CF3 CH₂Ph 5-39 3,4-diCl, 5-CF3CF3 H

TABLE 6

T² T³ m.p. °(C.) 6-1 CH3 CH3 6-2 CH3 CH2CH3 6-3 CH2CH3 CH2CH3 6-4 n-Prn-Pr 6-5 iso-Pr iso-Pr 6-6 cyclo-Pr cyclo-Pr 6-7 n-Bu n-Bu 6-8 tert-Butert-Bu 6-9 n-Pen n-Pen

TABLE 7

(X)m R Y R1 R2 W m.p. °(C.) 7-1 3,5-diCl CF3 H CF3CH2 H O 7-2 3,5-diClCF3 H 2-PyridylCH2 H O 7-3 3,5-diCl CF3 CH3 CF3CH2 H O 7-4 3,5-diCl CF3CH3 2-PyridylCH2 H O 7-5 3,5-diCl CF3 F CF3CH2 H O 7-6 3,5-diCl CF3 F2-PyridylCH2 H O 7-7 3,5-diCl CF3 Cl CF3CH2 H O 7-8 3,5-diCl CF3 Cl2-PyridylCH2 H O 7-9 3,5-diCl CF3 Br CF3CH2 H O 7-10 3,5-diCl CF3 Br2-PyridylCH2 H O 7-11 3,5-diCl CF3 Br cyclo-Pr H O 7-12 3,5-diCl CF3 BrNCCH2CH2 H O 7-13 3,5-diCl CF3 I CF3CH2 H O 7-14 3,5-diCl CF3 I2-PyridylCH2 H O 7-15 3,5-diCl CF3 NO2 CF3CH2 H O 7-16 3,5-diCl CF3 NO22-PyridylCH2 H O 7-17 3-Cl CF3 NO2 2-PyridylCH2 H O 7-18 3-Cl CF3 NO2CF3CH2 H O 7-19 3-Br CF3 NO2 2-PyridylCH2 H O 7-20 3-CF3 CF3 NO22-PyridylCH2 H O 7-21 3-CF3 CF3 NO2 CF3CH2 H O 7-22 3,5-diCF3 CF3 NO22-PyridylCH2 H O 7-23 3,5-diCF3 CF3 NO2 CF3CH2 H O 7-24 3-NO2 CF3 NO22-PyridylCH2 H O 7-25 3,5-diCl CF3 CF3 2-PyridylCH2 H O 7-26 3,5-diClCF3 CF3 CF3CH2 H O 7-27 3,5-diCl CF3 CH3O 2-PyridylCH2 H O 7-28 3,5-diClCF3 CN 2-PyridylCH2 H O 7-29 3,5-diCl CF3 CF3O 2-PyridylCH2 H O 7-303,5-diCl CF3 CH3S 2-PyridylCH2 H O 7-31 3,5-diCl CF3 CH3S(O)2-PyridylCH2 H O 7-32 3,5-diCl CF3 CH3S(O)2 2-PyridylCH2 H O 7-333,5-diCl CF3 CF3S 2-PyridylCH2 H O 7-34 3,5-diCl CF3 CF3S(O)2-PyridylCH2 H O 7-35 3,5-diCl CF3 CF3S(O)2 2-PyridylCH2 H O 7-363,5-diCl CF3 OH 2-PyridylCH2 H O 7-37 3,5-diCl CF3 SH 2-PyridylCH2 H O7-38 3,5-diCl CF3 NH2 2-PyridylCH2 H O 7-39 3,5-diCl CF3 NHCOCH32-PyridylCH2 H O 7-40 3,5-diCl CF3 NHCOCF3 2-PyridylCH2 H O 7-413,5-diCl CF3 NHCO2CH3 2-PyridylCH2 H O 7-42 3,5-diCl CF3 NHCO2CH2CCl32-PyridylCH2 H O 7-43 3-CH3 CF3 H 2-PyridylCH2 H O 7-44 3-CH3O CF3 H2-PyridylCH2 H O 7-45 3-CN CF3 H 2-PyridylCH2 H O 7-46 3-CF3O CF3 H2-PyridylCH2 H O 7-47 3-CH3S CF3 H 2-PyridylCH2 H O 7-48 3-CH3S(O) CF3 H2-PyridylCH2 H O 7-49 3-CH3S(O)2 CF3 H 2-PyridylCH2 H O 7-50 3-CF3S CF3H 2-PyridylCH2 H O 7-51 3-CF3S(O) CF3 H 2-PyridylCH2 H O 7-52 3-CF3S(O)2CF3 H 2-PyridylCH2 H O 7-53 3-OH CF3 H 2-PyridylCH2 H O 7-54 3-SH CF3 H2-PyridylCH2 H O 7-55 3,4-diCl CF3 H 2-PyridylCH2 H O 7-56 3,4-diCl CF3H CF3CH2 H O 7-57 3,4,5-triCl CF3 H 2-PyridylCH2 H O 7-58 3,4,5-triClCF3 H CF3CH2 H O 7-59 3,5-diBr CF3 H 2-PyridylCH2 H O 7-60 3,5-diBr CF3H CF3CH2 H O 7-61 3,5-diMe-4-NO2 CF3 H 2-PyridylCH2 H O 7-623,5-diMe-4-NO2 CF3 H CF3CH2 H O 7-63 3,5-diCl CF3 H 2-PyridylCH2 H S7-64 3,5-diCl CF3 NO2 H H O 7-65 3,5-diCl CF3 NO2 Me H O 7-66 3,5-diClCF3 NO2 iso-Pr H O 7-67 3,5-diCl CF3 NO2 PhCH2 H O 7-68 3,5-diCl CF3 NO2CH2CO2CH3 H O 7-69 3,5-diCl CF3 NO2 CH2CONMe H O 7-70 3,5-diCl CF3 NO2CH2(cyclo)Pr H O 7-71 3,5-diCl CF3 NO2 SO2Me H O 7-72 3,5-diCl CF3 NO2SO2CF3 H O 7-73 3,5-diCl CF3 NO2 CH2═CHCH2 H O 7-74 3,5-diCl CF3 NO2HCCCH2 H O 7-75 3,5-diCl CF3 NO2 CH2CN H O 7-76 3,5-diCl CF3 NO2C(Me)2CH2SCH3 H O 7-77 3,5-diCl CF3 NO2 2-F-Ph H O 7-78 3,5-diCl CH3 H2-PyridylCH2 H O 7-79 3,5-diCl CF3 H 2-PyridylCH2 CH3 O 7-80 3-NO2 CF3NO2 CF3CH2 H O 7-81 3,5-diCl CF3 Cl 2-PyridylCH2 H S 7-82 2-diCl CF3 NO22-PyridylCH2 H O 7-83 2,3-diCl CF3 NO2 2-PyridylCH2 H O 7-84 3,5-diClCF3 NO2 3-PyridylCH2 H O 7-85 3,5-diCl CF3 NO2 4-PyridylCH2 H O 7-863,5-diCl CF3 NO2 2-(6-Cl-pyridyl)CH2 H O 7-87 3,5-diCl CF3 NO23-(6-Cl-pyridyl)CH2 H O 7-88 3,5-diCl CF3 NO2 2-PyrinidinylCH2 H O 7-893,5-diCl CF3 NO2 1-(1-ethylpyrrolidin- H O 2-yl)CH2 7-90 3,5-diCl CF3CF3 CF3CH2 H O 7-91 3,5-diCl CF3 CF3 2-(6-Cl-pyridyl)CH2 H O 7-923,5-diCl CF3 NO2 Me2NCH═ O 7-93 3,5-diCl CF3 NO2 EtON═CH H O 7-943,5-diCl CF3 C═NOCH3 2-PyridylCH2 H O 7-95 4-Cl CF3 NO2 2-PyridylCH2 H O7-96 4-Cl CF3 NO2 CF3CH2 H O 7-97 3,5-diCl CF3 CN CF3CH2 H O 7-983,5-diCl CF3 CF3 H H O 7-99 3,5-diCF3 CF3 CF3 2-PyridylCH2 H O 7-1003,5-diCF3 CF3 CF3 CF3CH2 H O

TABLE 8

(X)m R Y R1 R2 W m.p. °(C.) 8-1 3,5-diCl CF3 CH3 CF3CH2 H O 8-2 3,5-diClCF3 CH3 2-PyridylCH2 H O 8-3 3,5-diCl CF3 F CF3CH2 H O 8-4 3,5-diCl CF3F 2-PyridylCH2 H O 8-5 3,5-diCl CF3 Cl CF3CH2 H O 8-6 3,5-diCl CF3 Cl2-PyridylCH2 H O 8-7 3,5-diCl CF3 Br CF3CH2 H O 8-8 3,5-diCl CF3 Br2-PyridylCH2 H O 8-9 3,5-diCl CF3 Br cyclo-Pr H O 8-10 3,5-diCl CF3 BrNCCH2CH2 H O 8-11 3,5-diCl CF3 I CF3CH2 H O 8-12 3,5-diCl CF3 I2-PyridylCH2 H O 8-13 3,5-diCl CF3 NO2 CF3CH2 H O 8-14 3,5-diCl CF3 NO22-PyridylCH2 H O 8-15 3-Cl CF3 NO2 2-PyridylCH2 H O 8-16 3-Cl CF3 NO2CF3CH2 H O 8-17 3-Br CF3 NO2 2-PyridylCH2 H O 8-18 3-CF3 CF3 NO22-PyridylCH2 H O 8-19 3-CF3 CF3 NO2 CF3CH2 H O 8-20 3,5-diCF3 CF3 NO22-PyridylCH2 H O 8-21 3,5-diCF3 CF3 NO2 CF3CH2 H O 8-22 3-NO2 CF3 NO22-PyridylCH2 H O 8-23 3,5-diCl CF3 CF3 2-PyridylCH2 H O 8-24 3,5-diClCF3 CF3 CF3CH2 H O 8-25 3,5-diCl CF3 CF3 H H O 8-26 3,5-diCl CF3 CH3O2-PyridylCH2 H O 8-27 3,5-diCl CF3 CN 2-PyridylCH2 H O 8-28 3,5-diCl CF3CF3O 2-PyridylCH2 H O 8-29 3,5-diCl CF3 CH3S 2-PyridylCH2 H O 8-303,5-diCl CF3 CH3S(O) 2-PyridylCH2 H O 8-31 3,5-diCl CF3 CH3S(O)22-PyridylCH2 H O 8-32 3,5-diCl CF3 CF3S 2-PyridylCH2 H O 8-33 3,5-diClCF3 CF3S(O) 2-PyridylCH2 H O 8-34 3,5-diCl CF3 CF3S(O)2 2-PyridylCH2 H O8-35 3,5-diCl CF3 OH 2-PyridylCH2 H O 8-36 3,5-diCl CF3 SH 2-PyridylCH2H O 8-37 3,5-diCl CF3 NH2 2-PyridylCH2 H O 8-38 3,5-diCl CF3 NHCOCH32-PyridylCH2 H O 8-39 3,5-diCl CF3 NHCOCF3 2-PyridylCH2 H O 8-403,5-diCl CF3 NHCO2CH3 2-PyridylCH2 H O 8-41 3,5-diCl CF3 NHCO2CH2CCl32-PyridylCH2 H O 8-42 3-CH3 CF3 H 2-PyridylCH2 H O 8-43 3-CH3O CF3 H2-PyridylCH2 H O 8-44 3-CN CF3 H 2-PyridylCH2 H O 8-45 3-CF3O CF3 H2-PyridylCH2 H O 8-46 3-CH3S CF3 H 2-PyridylCH2 H O 8-47 3-CH3S(O) CF3 H2-PyridylCH2 H O 8-48 3-CH3S(O)2 CF3 H 2-PyridylCH2 H O 8-49 3-CF3S CF3H 2-PyridylCH2 H O 8-50 3-CF3S(O) CF3 H 2-PyridylCH2 H O 8-51 3-CF3S(O)2CF3 H 2-PyridylCH2 H O 8-52 3-OH CF3 H 2-PyridylCH2 H O 8-53 3-SH CF3 H2-PyridylCH2 H O 8-54 3,4-diCl CF3 H 2-PyridylCH2 H O 8-55 3,4-diCl CF3H CF3CH2 H O 8-56 3,4,5-triCl CF3 H 2-PyridylCH2 H O 8-57 3,4,5-triClCF3 H CF3CH2 H O 8-58 3,5-diBr CF3 H 2-PyridylCH2 H O 8-59 3,5-diBr CF3H CF3CH2 H O 8-60 3,5-diMe-4-NO2 CF3 H 2-PyridylCH2 H O 8-613,5-diMe-4-NO2 CF3 H CF3CH2 H O 8-62 3,5-diCl CF3 H 2-PyridylCH2 H S8-63 3,5-diCl CF3 NO2 H H O 8-64 3,5-diCl CF3 NO2 Me H O 8-65 3,5-diClCF3 NO2 iso-Pr H O 8-66 3,5-diCl CF3 NO2 PhCH2 H O 8-67 3,5-diCl CF3 NO2CH2CO2CH3 H O 8-68 3,5-diCl CF3 NO2 CH2CONMe H O 8-69 3,5-diCl CF3 NO2CH2(cyclo)Pr H O 8-70 3,5-diCl CF3 NO2 SO2Me H O 8-71 3,5-diCl CF3 NO2SO2CF3 H O 8-72 3,5-diCl CF3 NO2 CH2═CHCH2 H O 8-73 3,5-diCl CF3 NO2HCCCH2 H O 8-74 3,5-diCl CF3 NO2 CH2CN H O 8-75 3,5-diCl CF3 NO2C(Me)2CH2SCH3 H O 8-76 3,5-diCl CF3 NO2 2-F-Ph H O 8-77 3,5-diCl CH3 H2-PyridylCH2 H O 8-78 3,5-diCl CF3 H 2-PyridylCH2 CH3 O 8-79 3-NO2 CF3NO2 CF3CH2 H O 8-80 3,5-diCl CF3 Cl 2-PyridylCH2 H S 8-81 2-diCl CF3 NO22-PyridylCH2 H O 8-82 2,3-diCl CF3 NO2 2-PyridylCH2 H O 8-83 3,5-diClCF3 NO2 3-PyridylCH2 H O 8-84 3,5-diCl CF3 NO2 4-PyridylCH2 H O 8-853,5-diCl CF3 NO2 2-(6-Cl-pyridyl)CH2 H O 8-86 3,5-diCl CF3 NO23-(6-Cl-pyridyl)CH2 H O 8-87 3,5-diCl CF3 NO2 2-PyrinidinylCH2 H O 8-883,5-diCl CF3 NO2 1-(1-ethylpyrrolidin- H O 2-yl)CH2 8-89 3,5-diCl CF3CF3 CF3CH2 H O 8-90 3,5-diCl CF3 CF3 2-(6-Cl-pyridyl)CH2 H O 8-913,5-diCl CF3 NO2 Me2NCH═ O 8-92 3,5-diCl CF3 NO2 EtON═CH H O 8-933,5-diCl CF3 C═NOCH3 2-PyridylCH2 H O 8-94 4-Cl CF3 NO2 2-PyridylCH2 H O8-95 4-Cl CF3 NO2 CF3CH2 H O 8-96 3,5-diCl CF3 CN CF3CH2 H O 8-973,5-diCl CF3 CF3 H H O 8-98 3,5-diCF3 CF3 CF3 2-PyridylCH2 H O 8-993,5-diCF3 CF3 CF3 CF3CH2 H O

TABLE 9

(X)m R Y R2 R3 R4 R5 I m.p. °(C.) 9-1 3,5-diCl CF3 H H H H COCH3 1 9-23,5-diCl CF3 H H H H COC2H5 1 9-3 3,5-diCl CF3 Cl H H H COCH3 1 9-43,5-diCl CF3 Br H H H COCH3 1 9-5 3,5-diCl CF3 Br H H H COC2H5 1 9-63,5-diCl CF3 Br H H H CO(i-Pr) 1 9-7 3,5-diCl CF3 Br H H H CO2-pyridyl 19-8 3,5-diCl CF3 F H H H COCH3 1 9-9 3,5-diCl CF3 I H H H COCH3 1 9-103,5-diCl CF3 NO2 H H H COCH3 1 9-11 3,5-diCl CF3 CH3 H H H COCH3 1 9-123,5-diCl CF3 MeS H H H COCH3 1 9-13 3,5-diCl CF3 MeSO H H H COCH3 1 9-143,5-diCl CF3 MeSO2 H H H COCH3 1 9-15 3,5-diCl CF3 CF3S H H H COCH3 19-16 3,5-diCl CF3 CF3S(O) H H H COCH3 1 9-17 3,5-diCl CF3 CF3S(O)2 H H HCOCH3 1 9-18 3,5-diCl CF3 OCH3 H H H COCH3 1 9-19 3,5-diCl CF3 OCF3 H HH COCH3 1 9-20 3.5-diCl CF3 OH H H H COCH3 1 9-21 3,5-diCl CF3 SH H H HCOCH3 1 9-22 3,5-diCl CF3 NH2 H H H COCH3 1 9-23 3,5-diCl CF3 NHCOCH3 HH H COCH3 1 9-24 3,5-diCl CF3 NHCO2CH3 H H H COCH3 1 9-25 3,5-diCl CF3NHCO2CH2CCl3 H H H COCH3 1 9-26 3,5-diCl CF3 Cl H H Me CO2-pyridyl 19-27 3,5-diCl CF3 Cl H H Me COCH3 1 9-28 3,5-diCl CF3 Cl H H Et COCH3 19-29 3,5-diCl CF3 Cl H H vinyl COCH3 1 9-30 3,5-diCl CF3 Cl H Hpropargyl COCH3 1 9-31 3,5-diCl CF3 Cl H H CH2Ph COCH3 1 9-32 3,5-diClCF3 Cl H H CN COCH3 1 9-33 3,5-diCl CF3 Cl H H CH2CF3 COCH3 1 9-343,5-diCl CF3 Cl H H cycloPr COCH3 1 9-35 3,5-diCl CF3 Cl H H COCH3 COCH31 9-36 3,5-diCl CF3 Cl H H H COC2H5 1 9-37 3,5-diCl CF3 Cl H H H COC2F51 9-38 3,5-diCl CF3 Cl H H H COPh 1 9-39 3,5-diCl CF3 Cl H H HCO2-pyridyl 1 9-40 3,5-diCl CF3 Cl H H H CONMe2 1 9-41 3,5-diCl CF3 Cl HH H CO2Me 1 9-42 3,5-diCl CF3 Cl H H H COSMe 1 9-43 3,5-diCl CF3 Cl H HMe COCH3 1 9-44 3,5-diCl CF3 Cl H H 2-pyridylCO COCH3 1 9-45 3,5-diBrCF3 Cl H H H COCH3 1 9-46 3-Cl CF3 Cl H H H COCH3 1 9-47 3-CF3 CF3 Cl HH H COCH3 1 9-48 3,5-diCF3 CF3 Cl H H H COCH3 1 9-49 3,4,5-triCl CF3 ClH H H COCH3 1 9-50 3,5-diMe-4-NO2 CF3 CI H H H COCH3 1 9-51 3-NO2 CF3 ClH H H COCH3 1 9-52 3-CH3 CF3 Cl H H H COCH3 1 9-53 3-CH3O CF3 Cl H H HCOCH3 1 9-54 3-CN CF3 Cl H H H COCH3 1 9-55 3-CF3O CF3 Cl H H H COCH3 19-56 3-CH3S CF3 Cl H H H COCH3 1 9-57 3-CH3S(O) CF3 Cl H H H COCH3 19-58 3-CH3S(O)2 CF3 Cl H H H COCH3 1 9-59 3-CF3S CF3 Cl H H H COCH3 19-60 3-CF3S(O) CF3 Cl H H H COCH3 1 9-61 3-CF3S(O)2 CF3 Cl H H H COCH3 19-62 3-OH CF3 Cl H H H COCH3 1 9-63 3-SH CF3 Cl H H H COCH3 1 9-643,5-diCl CF3 Cl CN H H COCH3 1 9-65 3,5-diCl CF3 Cl Me H H COCH3 1 9-663 5-diCl CF3 Cl Me Me H COCH3 1 9-67 3,5-diCl CF3 Cl cyclo-Pr H H COCH31 9-68 3,5-diCl CF3 Cl CF3 H H COCH3 1 9-69 3,5-diCl CF3 Cl CO2Me H HCOCH3 1 9-70 3,5-diCl CF3 Cl CH═CH2 H H COCH3 1 9-71 3,5-diCl CF3 ClCH2CH2 H COCH3 1 9-72 3,5-diCl CF3 Cl CCH H H COCH3 1 9-73 3,5-diCl CF3Br H H H COEt 1 9-74 3,5-diCl CF3 Br H H H COPr-n 1 9-75 3,5-diCl CF3 BrH H H COPr-iso 1 9-76 3,5-diCl CF3 Br H H H COBu-tert 1 9-77 3,5-diClCF3 Br H H H COCF3 1 9-78 3,5-diCl CF3 Br H H H COPh 1 9-79 3,5-diCl CF3Br H H H COpyridyl-2 1 9-80 3,5-diCl CF3 Br H H H COpyridyl-3 1 9-813,5-diCl CF3 Br H H H COpyridylCO-4 1 9-82 3,5-diCl CF3 Br H H HCOPh-F-2 1 9-83 3,5-diCl CF3 Br H H H COPh-F-3 1 9-84 3,5-diCl CF3 Br HH H COPh-F-4 1 9-85 3 5-diCl CF3 Br H H H COPh-Cl-2 1 9-86 3,5-diCl CF3Br H H H COPh-Cl-3 1 9-87 3,5-diCl CF3 Br H H H COPh-Cl-4 1 9-883,5-diCl CF3 Br H H H COPh-Br-2 1 9-89 3,5-diCl CF3 Br H H H COPh-Me-2 19-90 3,5-diCl CF3 Br H H H Covinyl 1 9-91 3,5-diCl CF3 Br H H HCOpropargyl 1 9-92 3,5-diCl CF3 Br H H H MeSO2 1 9-93 3,5-diCl CF3 Br HH H CF3SO2 1 9-94 3 5-diCl CF3 Br H H H CONHMe 1 9-95 3,5-diCl CF3 Br HH H CONMe2 1 9-96 3,5-diCl CF3 Br H H H CO2Me 1 9-97 3,5-diCl CF3 Br H HH C(O)SMe 1 9-98 3 5-diCl CF3 Br H H H CSMe 1 9-99 3,5-diCl CF3 Br H H HCON(Me)OMe 1 9-100 3,5-diCl CH3 Br H H H COCH3 1 9-101 3,5-diCl CH3 CF3H H H COCH3 1 9-102 3 5-diCl CH3 CN H H H COCH3 1 9-103 3,5-diCl CH3 NH2H H H COCH3 1 9-104 3,5-diCl CH3 NHCOCH3 H H H COCH3 1 9-105 3 5-diClCH3 NHCOCF3 H H H COCH3 1 9-106 3,5-diCl CH3 NHCO2CH3 H H H COCH3 19-107 3,5-diCl CH3 NHCO2CH2CCl3 H H H COCH3 1 9-108 3,5-diCl CH3NHSO2CH3 H H H COCH3 1 9-109 3,5-diCl CH3 NHSO2CF3 H H H COCH3 1 9-1103,5-diCl CH3 C═NOCH3 H H H COCH3 1 9-111 3,5-diCl CF3 Br H H H COCH3 29-112 3,5-diCF3 CF3 CF3 H H H COCH3 1 9-113 3,5-diCF3 CF3 CF3 H H HCOC2H5 1 9-114 3,5-diCF3 CF3 CF3 H H H COPr-cyclo 1 9-115 3,4,5-triClCF3 CF3 H H H COCH3 1 9-116 3,4,5-triCl CF3 CF3 H H H COC2H5 1 9-1173,4,5-triCl CF3 CF3 H H H COPr-cyclo 1 9-118 3,4,-diCl, 5-CF3 CF3 CF3 HH H COCH3 1

TABLE 10

(X)m R Y R2 R3 R4 R5 1 m.p. °(C.) 10-1 3,5-diCl CF3 Cl H H H COCH3 110-2 3,5-diCl CF3 Br H H H COCH3 1 10-3 3,5-diCl CF3 Br H H H COC2H5 110-4 3,5-diCl CF3 Br H H H CO(i-Pr) 1 10-5 3,5-diCl CF3 Br H H HCO2-pyridyl 1 10-6 3,5-diCl CF3 F H H H COCH3 1 10-7 3,5-diCl CF3 I H HH COCH3 1 10-8 3,5-diCl CF3 NO2 H H H COCH3 1 10-9 3,5-diCl CF3 CH3 H HH COCH3 1 10-10 3,5-diCl CF3 MeS H H H COCH3 1 10-11 3,5-diCl CF3 MeSO HH H COCH3 1 10-12 3,5-diCl CF3 MeSO2 H H H COCH3 1 10-13 3,5-diCl CF3CF3S H H H COCH3 1 10-14 3,5-diCl CF3 CF3S(O) H H H COCH3 1 10-153,5-diCl CF3 CF3S(O)2 H H H COCH3 1 10-16 3,5-diCl CF3 OCH3 H H H COCH31 10-17 3,5-diCl CF3 OCF3 H H H COCH3 1 10-18 3,5-diCl CF3 OH H H HCOCH3 1 10-19 3,5-diCl CF3 SH H H H COCH3 1 10-20 3,5-diCl CF3 NH2 H H HCOCH3 1 10-21 3,5-diCl CF3 NHCOCH3 H H H COCH3 1 10-22 3,5-diCl CF3NHCO2CH3 H H H COCH3 1 10-23 3,5-diCl CF3 NHCO2CH2CCl3 H H H COCH3 110-24 3,5-diCl CF3 Cl H H Me CO2-pyridyl 1 10-25 3,5-diCl CF3 Cl H H MeCOCH3 1 10-26 3,5-diCl CF3 Cl H H Et COCH3 1 10-27 3,5-diCl CF3 Cl H Hvinyl COCH3 1 10-28 3,5-diCl CF3 Cl H H propargyl COCH3 1 10-29 3,5-diClCF3 Cl H H CH2Ph COCH3 1 10-30 3,5-diCl CF3 Cl H H CN COCH3 1 10-313,5-diCl CF3 Cl H H CH2CF3 COCH3 1 10-32 3,5-diCl CF3 Cl H H cycloPrCOCH3 1 10-33 3,5-diCl CF3 Cl H H COCH3 COCH3 1 10-34 3,5-diCl CF3 Cl HH H COC2H5 1 10-35 3,5-diCl CF3 Cl H H H COC2F5 1 10-36 3,5-diCl CF3 ClH H H COPh 1 10-37 3,5-diCl CF3 Cl H H H CO2-pyridyl 1 10-38 3,5-diClCF3 Cl H H H CONMe2 1 10-39 3,5-diCl CF3 Cl H H H CO2Me 1 10-40 3,5-diClCF3 Cl H H H COSMe 1 10-41 3,5-diCl CF3 Cl H H Me COCH3 1 10-42 3,5-diClCF3 Cl H H 2-pyridylCO COCH3 1 10-43 3,5-diBr CF3 Cl H H H COCH3 1 10-443-Cl CF3 Cl H H H COCH3 1 10-45 3-CF3 CF3 Cl H H H COCH3 1 10-463,5-diCF3 CF3 Cl H H H COCH3 1 10-47 3,4,5-triCl CF3 Cl H H H COCH3 110-48 3,5-diMe-4-NO2 CF3 Cl H H H COCH3 1 10-49 3-NO2 CF3 Cl H H H COCH31 10-50 3-CH3 CF3 Cl H H H COCH3 1 10-51 3-CH3O CF3 Cl H H H COCH3 110-52 3-CN CF3 Cl H H H COCH3 1 10-53 3-CF3O CF3 Cl H H H COCH3 1 10-543-CH3S CF3 Cl H H H COCH3 1 10-55 3-CH3S(O) CF3 Cl H H H COCH3 1 10-563-CH3S(O)2 CF3 Cl H H H COCH3 1 10-57 3-CF3S CF3 Cl H H H COCH3 1 10-583-CF3S(O) CF3 Cl H H H COCH3 1 10-59 3-CF3S(O)2 CF3 Cl H H H COCH3 110-60 3-OH CF3 Cl H H H COCH3 1 10-61 3-SH CF3 Cl H H H COCH3 1 10-623,5-diCl CF3 Cl CN H H COCH3 1 10-63 3,5-diCl CF3 Cl Me H H COCH3 110-64 3,5-diCl CF3 Cl Me Me H COCH3 1 10-65 3,5-diCl CF3 Cl cyclo-Pr H HCOCH3 1 10-66 3,5-diCl CF3 Cl CF3 H H COCH3 1 10-67 3,5-diCl CF3 ClCO2Me H H COCH3 1 10-68 3,5-diCl CF3 Cl CH═CH2 H H COCH3 1 10-693,5-diCl CF3 Cl CH2CH2 H COCH3 1 10-70 3,5-diCl CF3 Cl CCH H H COCH3 110-71 3,5-diCl CF3 Br H H H COEt 1 10-72 3,5-diCl CF3 Br H H H COPr-n 110-73 3,5-diCl CF3 Br H H H COPr-iso 1 10-74 3,5-diCl CF3 Br H H HCOBu-tert 1 10-75 3,5-diCl CF3 Br H H H COCF3 1 10-76 3,5-diCl CF3 Br HH H COPh 1 10-77 3,5-diCl CF3 Br H H H COpyridyl-2 1 10-78 3,5-diCl CF3Br H H H COpyridyl-3 1 10-79 3,5-diCl CF3 Br H H H COpyridylCO-4 1 10-803,5-diCl CF3 Br H H H COPh-F-2 1 10-81 3,5-diCl CF3 Br H H H COPh-F-3 110-82 3,5-diCl CF3 Br H H H COPh-F-4 1 10-83 3,5-diCl CF3 Br H H HCOPh-Cl-2 1 10-84 3,5-diCl CF3 Br H H H COPh-Cl-3 1 10-85 3,5-diCl CF3Br H H H COPh-Cl-4 1 10-86 3,5-diCl CF3 Br H H H COPh-Br-2 1 10-873,5-diCl CF3 Br H H H COPh-Me-2 1 10-88 3,5-diCl CF3 Br H H H Covinyl 110-89 3,5-diCl CF3 Br H H H COpropargyl 1 10-90 3,5-diCl CF3 Br H H HMeSO2 1 10-91 3,5-diCl CF3 Br H H H CF3SO2 1 10-92 3,5-diCl CF3 Br H H HCONHMe 1 10-93 3,5-diCl CF3 Br H H H CONMe2 1 10-94 3,5-diCl CF3 Br H HH CO2Me 1 10-95 3,5-diCl CF3 Br H H H C(O)SMe 1 10-96 3,5-diCl CF3 Br HH H CSMe 1 10-97 3,5-diCl CF3 Br H H H CON(Me)OMe 1 10-98 3,5-diCl CH3Br H H H COCH3 1 10-99 3,5-diCl CH3 CF3 H H H COCH3 1 10-100 3,5-diClCH3 CN H H H COCH3 1 10-101 3,5-diCl CH3 NH2 H H H COCH3 1 10-1023,5-diCl CH3 NHCOCH3 H H H COCH3 1 10-103 3,5-diCl CH3 NHCOCF3 H H HCOCH3 1 10-104 3,5-diCl CH3 NHCO2CH3 H H H COCH3 1 10-105 3,5-diCl CH3NHCO2CH2CCl3 H H H COCH3 1 10-106 3,5-diCl CH3 NHSO2CH3 H H H COCH3 110-107 3,5-diCl CH3 NHSO2CF3 H H H COCH3 1 10-108 3,5-diCl CH3 C═NOCH3 HH H COCH3 1 10-109 3,5-diCl CF3 Br H H H COCH3 2 10-110 3,5-diCF3 CF3CF3 H H H COCH3 1 10-111 3,5-diCF3 CF3 CF3 H H H COC2H5 1 10-1123,5-diCF3 CF3 CF3 H H H COPr-cyclo 1 10-113 3,4,5-triCl CF3 CF3 H H HCOCH3 1 10-114 3,4,5-triCl CF3 CF3 H H H COC2H5 1 10-115 3,4,5-triCl CF3CF3 H H H COPr-cyclo 1 10-116 3,4,-diCl, 5-CF3 CF3 CF3 H H H COCH3 1

TABLE 11

(X)m R Y T⁴ m.p. °(C.) 11-1 3,5-diCl CF3 NO2 CO2Me 11-2 3,5-diCl CF3 NO2CO2H 11-3 3,5-diCl CF3 NH2 CO2Me 11-4 3,5-diCl CF3 F CO2Me 11-5 3,5-diClCF3 Cl CO2Me 11-6 3,5-diCl CF3 Cl CO2Bu-t 11-7 3,5-diCl CF3 Cl CO2H 11-83,5-diCl CF3 Br CO2Me 11-9 3,5-diCl CF3 I CO2Me 11-10 3,5-diCl CF3 CH3CO2Me 11-11 3,5-diCl CF3 Cl CH3 11-12 3,5-diCl CF3 CN F 11-13 3,5-diClCF3 CH3 NO2 11-14 3,5-diCl CF3 CH3 NH2 11-15 3,5-diCl CF3 Br NO2 11-163,5-diCl CF3 Br NH2 11-17 3-CF3 CF3 NO2 CO2Me 11-18 3-CF3 CF3 NO2 CO2H11-19 3,5-diCF3 CF3 NO2 CO2Me 11-20 3,5-diCF3 CF3 NO2 CO2H 11-213,4-diCl CF3 NO2 CO2Me 11-22 3,4-diCl CF3 NO2 CO2H 11-23 3-Cl CF3 NO2CO2Me 11-24 3-Cl CF3 NO2 CO2H 11-25 3,5-diBr CF3 NO2 CO2Me 11-263,4,5-triCl CF3 NO2 CO2Me 11-27 3,5-diMe-4-NO2 CF3 NO2 CO2Me 11-28 3-NO2CF3 NO2 CO2Me 11-29 3-CH3 CF3 NO2 CO2Me 11-30 3-CH3O CF3 NO2 CO2Me 11-313-CN CF3 NO2 CO2Me 11-32 3-CF3O CF3 NO2 CO2Me 11-33 3-CH3S CF3 NO2 CO2Me11-34 3-CH3S(O) CF3 NO2 CO2Me 11-35 3-CH3S(O)2 CF3 NO2 CO2Me 11-363-CF3S CF3 NO2 CO2Me 11-37 3-CF3S(O) CF3 NO2 CO2Me 11-38 3-CF3S(O)2 CF3NO2 CO2Me 11-39 3-OH CF3 NO2 CO2Me 11-40 3-SH CF3 NO2 CO2Me 11-41 3-NO2CF3 NO2 CO2H 11-42 3,4,5-triCl CF3 NO2 CO2H 11-43 2-Cl CF3 NO2 CO2Me11-44 2-Cl CF3 NO2 CO2H 11-45 4-Cl CF3 NO2 CO2Me 11-46 4-Cl CF3 NO2 CO2H11-47 3,5-diCl CF3 CF3 CO2Et 11-48 3,5-diCl CF3 CF3 CO2H 11-493,5-diMe-4-NO2 CF3 NO2 CO2H 11-50 3,4,5-triCl CF3 NO2 CO2Me 11-513,5-diCl CF3 CN CO2H 11-52 3,5-diCl CF3 CN CO2Me 11-53 3,5-diCF3 CF3 CF3CO2Et 11-54 3,5-diCl CF3 CF3 F 11-55 3,5-diCl CF3 CF3 NO2 11-56 3,5-diClCF3 CF3 NH2 11-57 3,5-diCl CF3 F CO2Et 11-58 3,4,5-triCl CF3 CF3 CO2Et11-59 3,4,5-triCl CF3 CF3 CO2H

TABLE 12

(X)m R Y T⁴ m.p. °(C.) 12-1 3,5-diCl CF3 H NO2 12-2 3,5-diCl CF3 H CN12-3 3,5-diCl CF3 H NH2 12-4 3,5-diCl CF3 H CO2Me 12-5 3,5-diCl CF3 HCO2H 12-6 3,5-diCl CF3 NO2 CO2Me 12-7 3,5-diCl CF3 NO2 CO2H 12-83,5-diCl CF3 NH2 CO2Me 12-9 3,5-diCl CF3 F CO2Me 12-10 3,5-diCl CF3 ClCO2Me 12-11 3,5-diCl CF3 Cl CO2Bu-t 12-12 3,5-diCl CF3 Cl CO2H 12-133,5-diCl CF3 Br CO2Me 12-14 3,5-diCl CF3 I CO2Me 12-15 3,5-diCl CF3 CH3CO2Me 12-16 3,5-diCl CF3 Cl CH3 12-17 3,5-diCl CF3 CN F 12-18 3,5-diClCF3 CH3 NO2 12-19 3,5-diCl CF3 CH3 NH2 12-20 3,5-diCl CF3 Br NO2 12-213,5-diCl CF3 Br NH2 12-22 3-CF3 CF3 NO2 CO2Me 12-23 3-CF3 CF3 NO2 CO2H12-24 3,5-diCF3 CF3 NO2 CO2Me 12-25 3,5-diCF3 CF3 NO2 CO2H 12-263,4-diCl CF3 NO2 CO2Me 12-27 3,4-diCl CF3 NO2 CO2H 12-28 3-Cl CF3 NO2CO2Me 12-29 3-Cl CF3 NO2 CO2H 12-30 3,5-diBr CF3 NO2 CO2Me 12-313,4,5-triCl CF3 NO2 CO2Me 12-32 3,5-diMe-4-NO2 CF3 NO2 CO2Me 12-33 3-NO2CF3 NO2 CO2Me 12-34 3-CH3 CF3 NO2 CO2Me 12-35 3-CH3O CF3 NO2 CO2Me 12-363-CN CF3 NO2 CO2Me 12-37 3-CF3O CF3 NO2 CO2Me 12-38 3-CH3S CF3 NO2 CO2Me12-39 3-CH3S(O) CF3 NO2 CO2Me 12-40 3-CH3S(O)2 CF3 NO2 CO2Me 12-413-CF3S CF3 NO2 CO2Me 12-42 3-CF3S(O) CF3 NO2 CO2Me 12-43 3-CF3S(O)2 CF3NO2 CO2Me 12-44 3-OH CF3 NO2 CO2Me 12-45 3-SH CF3 NO2 CO2Me 12-46 3-NO2CF3 NO2 CO2H 12-47 3,4,5-triCl CF3 NO2 CO2H 12-48 2-Cl CF3 NO2 CO2Me12-49 2-Cl CF3 NO2 CO2H 12-50 4-Cl CF3 NO2 CO2Me 12-51 4-Cl CF3 NO2 CO2H12-52 3,5-diCl CF3 CF3 CO2Et 12-53 3,5-diCl CF3 CF3 CO2H 12-543,5-diMe-4-NO2 CF3 NO2 CO2H 12-55 3,4,5-triCl CF3 NO2 CO2Me 12-563,5-diCl CF3 CN CO2H 12-57 3,5-diCl CF3 CN CO2Me 12-58 3,5-diCF3 CF3 CF3CO2Et 12-59 3,5-diCl CF3 CF3 F 12-60 3,5-diCl CF3 CF3 NO2 12-61 3,5-diClCF3 CF3 NH2 12-62 3,5-diCl CF3 F CO2Et 12-63 3,4,5-triCl CF3 CF3 CO2Et12-64 3,4,5-triCl CF3 CF3 CO2H

TABLE 13 1H-NMR 1-2  1H-NMR (CDCl3) δ: 2.50-2.60 (1H, m), 2.83-2.91 (1H,m), 3.49-3.65 (2H, m), 3.82 (1H, d), 4.12 (1H, d), 4.75 (2H, d), 6.61(2H, d), 7.21 (1H, dd), 7.29 (2H, d), 7.33-7.40 (3H, m), 7.68 (1H, td),1-3  1H-NMR (CDCl3) δ: 2.51-2.56 (4H, m), 2.83-2.87 (1H, m), 3.50-3.56(2H, m), 3.78 (1H, d), 4.00- 4.15 (3H, m), 6.03 (1H, br s), 6.38-6.41(2H, m), 7.26-7.39 (4H, m). 1-4  1H-NMR (CDCl3) δ: 2.49-2.55 (4H, m),2.80-2.88 (1H, m), 3.50-3.56 (2H, m), 3.78 (1H, d), 4.08 (1H, d), 4.71(2H, d), 6.39-6.41 (2H, m), 7.10-7.18 (2H, m), 7.32-7.43 (4H, m),7.65-7.68 (1H, m), 1-6  1H-NMR (CDCl3) δ: 2.50-2.63 (1H, m), 2.86-2.90(1H, m), 3.53-3.58 (2H, m), 3.78-3.81 (1H, m), 4.10-4.14 (1H, m), 4.78(2H, d), 6.23-6.28 (1H, m), 6.43-6.46 (1H, m), 7.17-7.40 (5H, m), 7.67-1-7  1H-NMR (CDCl3) δ: 2.55-2.57 (1H, m), 2.87-2.88 (1H, m), 3.51-3.61(2H, m), 3.80 (1H, d), 4.08- 4.19 (3H, m), 6.53-6.56 (2H, m), 6.87-6.91(1H, m), 7.26-7.27 (1H, m), 7.39-7.42 (1H, m), 7.85- 1-8  1H-NMR (CDCl3)δ: 2.53-2.60 (1H, m), 2.86-2.90 (1H, m), 3.53-3.56 (2H, m), 3.79 (1H,d), 4.09 (1H, d), 4.80 (2H, d), 6.52-6.56 (2H, m), 7.20-7.27 (2H, m),7.38-7.39 (2H, m), 7.70-7.73 (2H, m), 1-9  1H-NMR (CDCl3) δ: 2.56-2.58(1H, m), 2.85-2.93 (1H, m), 3.51-3.58 (2H, m), 3.78 (1H, d), 4.10- 4.14(3H, m), 6.56-6.61 (2H, m), 6.75-6.76 (1H, m), 7.26-7.29 (1H, m),7.40-7.40 (1H, m), 7.69 1-10 1H-NMR (CDCl3) δ: 2.53-2.60 (1H, m),2.85-2.90 (1H, m), 3.46-3.59 (2H, m), 3.78 (1H, d), 4.08 (1H, d), 4.77(2H, d), 6.55-6.56 (1H, m), 6.75-6.78 (1H, m), 7.18-7.44 (5H, m),7.65-7.70 (2H, m), 1-11 1H-NMR (CDCl3) δ: 0.62-0.65 (2H, m), 0.83-0.89(2H, m), 2.54-2.61 (1H, m), 2.86-2.90 (2H, m), 3.47-3.57 (2H, m), 3.76(1H, d), 4.06 (1H, d), 6.34 (1H, br s), 6.52-6.55 (1H, m), 6.71 (1H, d),1-12 1H-NMR (CDCl3) δ: 2.55-2.60 (1H, m), 2.74 (2H, t, J = 6.3 Hz),2.86-2.90 (1H, m), 3.50-3.57 (2H, m), 3.67-3.79 (3H, m), 4.08 (1H, d),6.53-6.56 (1H, m), 6.74-6.81 (2H, m), 7.27-7.27 (1H, m), 1-15 1H-NMR(CDCl3) δ: 2.56-2.66 (1H, m), 2.90-2.98 (1H, m), 3.52-3.68 (2H, m), 3.83(1H, d), 4.04- 4.16 (3H, m), 6.09 (1H, t), 6.75 (1H, dd), 7.10 (1H, d),7.28 (2H, d), 7.40-7.43 (2H, m). 1-16 1H-NMR (CDCl3) δ: 2.54-2.65 (1H,m), 2.89-2.97 (1H, m), 3.51-3.67 (2H, m), 3.83 (1H, d), 4.13 (1H, d),4.74 (2H, d), 6.75 (1H, dd), 7.08 (1H, d), 7.15-7.23 (2H, m), 7.28 (2H,br s), 7.37 (1H, d), 1-17 1H-NMR (CDCl3) δ: 2.57-2.67 (1H, m), 2.88-2.98(1H, m), 3.49-3.67 (2H, m), 3.87 (1H, d), 4.15 (1H, d), 4.75 (2H, d),6.74 (1H, dd), 7.08 (1H, d), 7.14 (1H, t), 7.21 (1H, dd), 7.26-7.38 (5H,m), 1-18 1H-NMR (CDCl3) δ: 2.58-2.68 (1H, m), 2.91-3.00 (1H, m),3.50-3.68 (2H, m), 3.87 (1H, d), 4.04- 4.17 (3H, m), 6.06 (1H, t), 6.75(1H, d), 7.10 (1H, s), 7.26-7.42 (5H, m). 1-21 1H-NMR (CDCl3) δ:2.61-2.72 (1H, m), 2.98-3.06 (1H, m), 3.53-3.70 (2H, m), 3.90 (1H, d),4.09 (2H, dt), 4.22 (1H, d), 6.08 (1H, t), 6.76 (1H, dd), 7.11 (1H, d),7.42 (1H, d), 7.57-7.69 (4H, m). 1-22 1H-NMR (CDCl3) δ: 2.62-2.73 (1H,m), 3.03-3.11 (1H, m), 3.57-3.73 (2H, m), 3.89 (1H, d), 4.27 (1H, d),4.75 (2H, d), 6.79 (1H, dd), 7.12 (1H, d), 7.16-7.24 (2H, m), 7.37 (1H,d), 7.51 (1H, d), 7.70 (1H, td), 7.84 (2H, br s), 7.95 (1H, br s), 8.52(1H, d). 1-23 1H-NMR (CDCl3) δ: 2.63-2.73 (1H, m), 3.04-3.13 (1H, m),3.58-3.74 (2H, m), 3.89 (1H, d), 4.10 (2H, td), 4.28 (1H, d), 6.07 (1H,t), 6.80 (1H, dd), 7.15 (1H, d), 7.43 (1H, d), 7.83 (2H, br s), 7.951-25 1H-NMR (CDCl3) δ: 2.54-2.61 (1H, m), 2.86-2.94 (1H, m), 3.52-3.64(2H, m), 3.81 (1H, d), 4.11 (1H, d), 4.72 (2H, d), 6.69-6.72 (1H, m),6.82-6.83 (1H, m), 7.15-7.40 (5H, m), 7.50-7.53 (1H, m), 1-27 1H-NMR(CDCl3) δ: 2.55-2.63 (1H, m), 2.90-2.94 (1H, m), 3.55-3.62 (2H, m),3.81-3.87 (1H, m), 4.11-4.14 (1H, m), 4.78 (2H, d), 6.76-6.79 (1H, m),6.87-6.88 (1H, m), 7.26-7.35 (5H, m), 7.57- 7.60 (1H, m), 7.68-7.70 (1H,m), 7.79-7.82 (1H, m), 8.55-8.57 (1H, 1-31 1H-NMR (CDCl3) δ: 2.53-2.63(1H, m), 2.88-2.96 (1H, m), 3.45 (3H, s), 3.56-3.68 (2H, m), 3.82- 3.86(1H, m), 4.14-4.17 (1H, m), 4.74 (2H, d, J = 5.1 Hz), 6.72-6.75 (1H, m),7.18-7.21 (1H, m), 7.28-7.29 (4H, m), 7.36-7.41 (2H, m), 7.53-7.55 (1H,m), 7.67-7. 1-38 1H-NMR (CDCl3) δ: 2.46-2.56 (1H, m), 2.78-2.87 (1H, m),3.49-3.57 (2H, m), 3.77 (1H, d), 4.06 (1H, d), 4.70 (2H, d), 5.79 (2H,d), 5.97-6.00 (1H, m), 7.18-7.41 (7H, m), 7.65-7.68 (1H, m), 8.56 1-391H-NMR (CDCl3) δ: 2.53-2.61 (1H, m), 2.84-2.92 (1H, m), 3.55-3.67 (2H,m), 3.83 (1H, d), 4.15 (1H, d), 4.72 (2H, d), 6.36-6.39 (1H, m),7.25-7.36 (4H, m), 7.64-7.70 (2H, m), 7.92-7.95 (2H, m), 1-54 1H-NMR(CDCl3) δ: 2.55-2.64 (1H, m), 2.89-2.94 (1H, m), 3.49-3.66 (2H, m), 3.84(1H, d), 4.13 (1H, d), 4.74 (2H, d), 6.74 (1H, dd), 7.07 (1H, d),7.16-7.27 (3H, m), 7.36 (1H, d), 7.47-7.52 (3H, 1-56 1H-NMR (CDCl3) δ:2.55-2.62 (1H, m), 2.88-2.96 (1H, m), 3.52-3.67 (2H, m), 3.82 (1H, d),4.12 (1H, d), 4.74 (2H, d), 6.75 (1H, dd), 7.08 (1H, d), 7.21 (2H, t),7.36 (1H, d), 7.42 (2H, s), 7.49 (1H, 1-57 1H-NMR (CDCl3) δ: 2.54-2.66(1H, m), 2.89-2.97 (1H, m), 3.53-3.69 (2H, m), 3.82 (1H, d), 4.03- 4.15(3H, m), 6.08 (1H, br s), 6.75 (1H, dd), 7.10 (1H, s), 7.40-7.42 (3H,m). 1-60 1H-NMR (CDCl3) δ: 2.36 (6H, s), 2.56-2.66 (1H, m), 2.91-2.99(1H, m), 3.51-3.67 (2H, m), 3.85 (1H, d), 4.15 (1H, d), 4.74 (2H, d, J =4.9 Hz), 6.75 (1H, dd), 7.09 (1H, d), 7.15-7.23 (4H, m), 7.37 1-611H-NMR (CDCl3) δ: 2.37 (6H, s), 2.57-2.68 (1H, m), 2.92-3.00 (1H, m),3.52-3.68 (2H, m), 3.86 (1H, d), 4.03-4.18 (3H, m), 6.09 (1H, t,), 6.75(1H, dd), 7.11 (1H, d), 7.15 (2H, s), 7.41 (1H, d). 1-63 1H-NMR(acetone-d6) δ: 2.72-2.85 (1H, m), 3.03-3.07 (1H, m), 3.63-3.71 (2H, m),4.04 (1H), 4.38 (1H, d), 6.58 (1H, br s), 6.85-6.88 (1H, m), 7.02 (1H,d), 7.23 (1H, br s), 7.53-7.59 (4H, m). 1-73 1H-NMR (CDCl3) δ: 2.09 (1H,s), 2.58-2.62 (1H, m), 2.90-2.94 (1H, m), 3.57-3.61 (2H, m), 3.83 (1H,d), 4.13 (1H), 4.22 (2H, q), 6.04 (1H, br s), 6.73-6.75 (1H, m), 7.07(1H, d), 7.27-7.28 (2H, 1-74 1H-NMR (acetone-d6) δ: 2.77-2.85 (1H, m),3.08-3.10 (1H, m), 3.66-3.68 (2H, m), 4.09 (1H, d), 4.33-4.46 (3H, m),6.94-6.97 (1H, m), 7.14 (1H, d), 7.55-7.63 (3H, m), 8.20-8.23 (1H, m).1-75 1H-NMR (CDCl3) δ: 1.50 (6H, s), 2.17 (3H, s), 2.57-2.62 (1H, m),2.90-2.94 (1H, m), 3.02 (2H, s), 3.56-3.59 (2H, m), 3.82 (1H, d), 4.11(1H, d), 5.82 (1H, br s), 6.71-6.73 (1H, m), 7.05 (1H, d), 1-78 1H-NMR(CDCl3) δ: 2.54-2.64 (1H, m), 2.87-2.95 (1H, m), 3.53-3.69 (2H, m), 3.85(1H, d), 4.15 (1H, d), 4.79 (2H, d), 6.95 (1H, dd), 7.17-7.21 (1H, m),7.28 (2H, s), 7.35 (1H, d), 7.41 (1H, t), 7.65 (1H, td), 7.96 (1H, d),8.10 (1H, d), 8.66-8.58 (2H, m). 1-80 1H-NMR (CDCl3) δ: 2.64-2.75 (1H,m), 3.02-3.10 (1H, m), 3.54-3.73 (2H, m), 3.93 (1H, d), 4.04- 4.15 (2H,m), 4.25 (1H, d), 6.04 (1H, t), 6.78 (1H, dd), 7.13 (1H, d), 7.43 (1H,d), 7.65 (1H, t), 7.76 1-81 1H-NMR (CDCl3) δ: 2.51-2.61 (1H, m),2.84-2.92 (1H, m), 3.45-3.61 (2H, m), 3.79 (1H, d), 4.08 (1H, d), 5.08(2H, d), 6.49-6.54 (2H, m), 7.22-7.28 (3H, m), 7.36 (1H, d), 7.40 (1H,t), 7.72 (1H, 1-82 1H-NMR (CDCl3) δ: 2.65-2.77 (1H, m), 3.18-3.26 (1H,m), 3.59 (2H, d), 3.99 (1H, d), 4.48 (1H, d), 4.75 (2H, d), 6.76 (1H,dd), 7.08-7.51 (9H, m), 7.70 (1H, td), 8.53 (1H, d). 1-83 1H-NMR (CDCl3)δ: 2.65-2.76 (1H, m), 3.18-3.25 (1H, m), 3.59 (2H, d), 3.99 (1H, d),4.49 (1H, d), 4.74 (2H, d), 6.76 (1H, dd), 7.07-7.38 (6H, m), 7.53 (2H,dt), 7.70 (1H, td), 8.52 (1H, d). 1-84 1H-NMR (CDCl3) δ: 2.61-2.64 (1H,m), 2.89-2.93 (1H, m), 3.57-3.60 (2H, m), 3.82 (1H, d), 4.12 (1H, d),4.62 (2H, d), 6.42 (1H, br s), 6.71-6.74 (1H, m), 7.06 (1H, d),7.27-7.42 (5H, m), 7.79 (1H, 1-85 1H-NMR (CDCl3) δ: 2.57-2.63 (1H, m),2.88-2.94 (1H, m), 3.54-3.63 (2H, m), 3.82 (1H, d), 4.13 (1H, d), 4.59(2H, d), 6.64-6.74 (2H, m), 7.05 (1H, d), 7.28 (4H, d), 7.41-7.43 (2H,m), 8.51-8.53 1-86 1H-NMR (CDCL3) δ: 2.55-2.65 (1H, m), 2.89-2.97 (1H,m), 3.56-3.68 (2H, m), 3.83 (1H, d), 4.14 (1H, d), 4.72 (2H, d),6.74-6.79 (2H, m) 7.09-7.10 (1H, m), 7.25-7.50 (5H, m), 7.68 (1H, t).1-87 1H-NMR (CDCl3) δ: 2.57-2.65 (1H, m), 2.90-2.95 (1H, m), 3.50-3.62(2H, m), 3.82 (1H, d), 4.12 (1H, d), 4.53 (2H, d), 6.66-6.70 (2H, m),7.02 (1H, d), 7.25-7.41 (5H, m), 7.72-7.74 (1H, m), 8.26 1-88 1H-NMR(CDCl3) δ: 2.58-2.63 (1H, m), 2.91-2.95 (1H, m), 3.53-3.68 (2H, m), 3.84(1H, d), 4.14 (1H, d), 4.88 (2H, d), 6.75-6.78 (1H, m), 7.08 (1H, d),7.20-7.29 (4H, m), 7.41-7.41 (1H, m), 7.55 1-90 1H-NMR (CDCl3) δ:2.56-2.61 (1H, m), 2.87-2.95 (1H, m), 3.53-3.65 (2H, m), 3.81 (1H, d),3.99- 4.13 (3H, m), 6.20-6.22 (1H, m), 6.68-6.71 (1H, m), 6.81 (1H, d),7.27-7.28 (2H, m), 7.40-7.41 1-91 1H-NMR (CDCl3) δ: 2.55-2.60 (1H, m),2.88-2.92 (1H, m), 3.52-3.65 (2H, m), 3.81 (1H, d), 4.11 (1H, d) 4.67(2H, d), 6.74-6.82 (3H, m), 7.23-7.28 (4H, m), 7.38-7.39 (1H, m), 7.50(1H, d), 7.64 1-92 1H-NMR (CDCl3) δ: 2.55-2.62 (1H, m), 2.86-2.94 (1H,m), 3.12 (6H, d), 3.53-3.63 (2H, m), 3.82 (1H, d), 4.13 (1H, d),6.62-6.67 (2H, m), 7.25-7.28 (1H, m), 7.40 (1H, d), 8.04 (1H, d), 8.54(1H, 1-93 1H-NMR (CDCl3) δ: 1.28 (3H, t), 2.59-2.64 (1H, m), 2.93-2.97(1H, m), 3.58-3.67 (2H, m), 3.85 (1H, d), 4.10-4.18 (3H, m), 6.75-6.78(1H, m), 7.09-7.50 (4H, m), 7.70-7.72 (1H, m), 8.47-8.50 1-95 1H-NMR(CDCl3) δ: 2.55-2.65 (1H, m), 2.88-2.97 (1H, m), 3.47-3.65 (2H, m), 3.86(1H, d), 4.14 (1H, d), 4.73 (2H, d), 6.73 (1H, dd), 7.06 (1H, d),7.23-7.15 (2H, m), 7.31-7.41 (5H, m), 7.48 (1H, 1-96 1H-NMR (CDCl3) δ:2.56-2.67 (1H, m), 2.90-2.99 (1H, m), 3.48-3.67 (2H, m), 3.86 (1H, d),4.03- 4.16 (3H, m), 6.06 (1H, br s), 6.73 (1H, dd), 7.09 (1H, d), 7.33(2H, d), 7.38-7.42 (3H, m). 1-97 1H-NMR (CDCl3) δ: 2.58-2.63 (1H, m),2.91-2.96 (1H, m), 3.55-3.67 (2H, m), 3.81-3.84 (1H, m), 4.07-4.18 (3H,m), 6.70-6.80 (3H, m), 7.27-7.42 (3H, m), 7.75-7.78 (1H, m) 1-98 1H-NMR(CDCl3) δ: 2.53-2.63 (1H, m), 2.89-2.92 (1H, m), 3.21-3.35 (1H, m),3.59-3.78 (3H, m), 4.10-4.13 (1H, m), 5.94-5.97 (2H, m), 6.73-6.85 (2H,m), 7.23-7.56 (4H, m) 1-99 1H-NMR (CDCl3) δ: 2.63-2.68 (1H, m),3.02-3.07 (1H, m), 3.55-3.71 (2H, m), 3.86-3.90 (1H, m), 4.23-4.26 (1H,m), 4.74 (2H, d), 6.74-6.77 (1H, m), 6.86-6.86 (1H, m), 7.07-7.10 (1H,m), 7.20- 7.22 (1H, m), 7.31-7.34 (1H, m), 7.53-7.56 (1H, m), 7.68-7.70(1H,  1-100 1H-NMR (CDCl3) δ: 2.65-2.67 (1H, m), 3.02-3.10 (1H, m),3.59-3.66 (2H, m), 3.86-3.90 (1H, m), 4.11-4.20 (3H, m), 5.99-6.02 (1H,m), 6.76-6.85 (2H, m), 7.50-7.53 (1H, m), 7.84-7.95 (3H, m),  1-1011H-NMR (CDCl3) δ: 2.54-2.64 (1H, m), 2.89-2.97 (1H, m), 3.54-3.70 (2H,m), 3.85 (1H, d), 4.04- 4.18 (3H, m), 6.94 (1H, dd), 7.29 (2H, s), 7.41(1H, t), 7.92 (1H, d), 8.14-8.06 (2H, m).  1-102 1H-NMR (CDCl3) δ:2.46-2.61 (1H, m), 2.83-2.91 (1H, m), 3.50-3.60 (2H, m), 3.77-3.81 (1H,m), 4.07-4.10 (1H, m), 4.70 (2H, d, J = 4.9 Hz), 6.67-6.70 (1H, m),6.80-6.81 (1H, m), 7.15-7.17 (2H, m), 7.30-7.32 (1H, m), 7.40-7.43 (2H,m), 7.48-7.51 (1H, m), 7. 2-8  1H-NMR (CDCl3) δ: 2.54-2.65 (1H, m),2.88-2.96 (1H, m), 3.50-3.68 (2H, m), 3.84 (1H, d), 4.13 (1H, d), 6.71(2H, d), 7.30 (2H, d), 7.41 (1H, t), 7.54 (2H, d), 8.85 (1H, s). 2-291H-NMR (CDCl3) δ: 2.14 (3H, s), 2.54-2.64 (1H, m), 2.87-2.95 (1H, m),3.49-3.65 (2H, m), 3.83 (1H, d), 4.12 (1H, d), 6.51-6.54 (2H, m), 7.17(1H, d), 7.30 (2H, d), 7.41 (1H, t), 8.68 (1H, s). 2-31 1H-NMR (CDCl3)δ: 2.59-2.69 (1H, m), 2.92-3.01 (1H, m), 3.57-3.73 (2H, m), 3.88 (1H,d), 4.18 (1H, d), 6.83 (1H, dd), 6.94 (1H, d), 7.44-7.30 (4H, m), 8.73(1H, s). 2-40 1H-NMR (DMSO-d6) δ: 2.62-2.73 (1H, m), 2.95-3.03 (1H, m),3.49-3.55 (2H, m), 3.90 (1H, d), 4.31 (1H, d), 7.09 (1H, dd), 7.29 (1H,d), 7.61 (1H, d), 7.68 (2H, d), 7.71 (1H, t), 8.26 (1H, s), 8.98 3-3 1H-NMR (CDCl3) δ: 1.99 (3H, s), 2.50-2.58 (1H, m), 2.82-2.87 (1H, m),3.45-3.51 (2H, m), 3.74 (1H, d), 4.02 (1H, d), 4.41 (2H, d), 6.43-6.46(1H, m), 6.58 (1H, d), 7.26-7.38 (4H, m). 3-4  1H-NMR (CDCl3) δ:1.98-2.02 (3H, m), 2.53-2.61 (1H, m), 2.81-2.89 (1H, m), 3.46-3.52 (2H,m), 3.74 (1H, d), 4.02 (1H), 4.42-4.44 (2H, m), 5.78-5.81 (1H, m),6.49-6.51 (1H, m), 6.77 (1H, d), 3-11 1H-NMR (CDCl3) δ: 2.13-2.18 (3H,m), 2.51-2.53 (1H, m), 2.81-2.83 (1H, m), 3.45-3.56 (2H, m), 3.75-3.78(1H, m), 4.01-4.04 (1H, m), 4.25 (1H, s), 4.57 (1H, s), 6.40-6.44 (2H,m), 6.93-6.96 (1H,  3-102 1H-NMR (CDCl3) δ: 2.03 (3H, s), 2.53-2.60 (1H,m), 2.83-2.91 (1H, m), 3.51-3.59 (2H, m), 3.78- 3.82 (1H, m), 4.07-4.13(1H, m), 4.50.55 (2H, m), 5.72-5.76 (1H, m), 6.70-6.78 (2H, m), 7.27- 3-113 1H-NMR (CDCl3) δ: 1.99 (3H, s), 2.58-2.68 (1H, m), 2.99-3.03 (1H,m), 3.51-3.67 (2H, m), 3.83- 3.86 (1H, m), 4.18-4.21 (1H, m), 4.50 (2H,d), 5.73-5.76 (1H, m), 6.74-6.81 (2H, m), 7.47-7.50 4-1  1H-NMR (CDCl3)δ: 2.56-2.64 (1H, m), 2.89-2.98 (1H, m), 3.63-3.67 (2H, m), 3.87 (1H,d), 4.19 (1H, d), 6.57 (2H, d), 7.27 (2H, br s), 7.42 (1H, t), 8.18 (2H,d). 4-2  1H-NMR (CDCl3) δ: 2.51-2.62 (1H, m), 2.86-2.94 (1H, m),3.56-3.61 (2H, m), 3.80 (1H, d), 4.12 (1H, d), 6.59 (2H, d), 7.26 (2H,br s), 7.41 (1H, t), 7.52 (2H, d). 4-3  1H-NMR (CDCl3) δ: 2.45-2.54 (1H,m), 2.74-2.82 (1H, m), 3.34-3.47 (4H, m), 3.73 (1H, d), 3.93 (1H, d),6.49-6.51 (2H, m), 6.67-6.71 (2H, m), 7.30 (2H, br s), 7.36 (1H, t).4-5  1H-NMR (DMSO-d6) δ: 2.58-2.72 (1H, m), 2.88-3.01 (1H, m), 3.41-3.53(2H, m), 3.85 (1H, d), 4.26 (1H, d), 6.71 (2H, d), 7.65-7.72 (3H, m),7.78 (2H, d), 12.25 (1H, br s). 4-6  1H-NMR (CDCl3) δ: 2.53-2.67 (1H,m), 2.89-2.97 (1H, m), 3.50-3.71 (2H, m), 3.83 (1H, d), 3.85 (3H, s),4.15 (1H, d), 6.69 (1H, dd), 6.75 (1H, d), 7.26 (3H, s), 7.42 (1H, t),7.81 (1H, d). 4-7  1H-NMR (DMSO-d6) δ: 2.58-2.72 (1H, m), 2.91-3.04 (1H,m), 3.47-3.57 (2H, m), 3.87 (1H, d), 4.32 (1H, d), 6.86 (1H, dd), 7.04(1H, d), 7.65 (2H, d), 7.71 (1H, t), 7.78 (1H, d). 4-8  1H-NMR (CDCl3)δ: 2.46-2.56 (1H, m), 2.79-2.85 (1H, m), 3.52-3.57 (2H, m), 3.76-3.86(4H, m), 4.01-4.12 (1H, m), 5.68-5.76 (2H, m), 5.87-5.99 (1H, m),6.26-6.32 (2H, m), 7.38-7.41 (1H, m), 4-10 1H-NMR (CDCl3) δ: 2.53-2.58(1H, m), 2.86-2.92 (1H, m), 3.52-3.62 (2H, m), 3.80 (1H, d), 3.87 (3H,s), 4.11 (1H, d), 6.45-6.48 (1H, m), 6.61 (1H, d), 7.26-7.27 (2H, m),7.40-7.41 (1H, m), 7.88 4-11 1H-NMR (CDCl3) δ: 1.59 (9H, s), 2.54-2.56(1H, m), 2.84-2.92 (1H, m), 3.53-3.56 (2H, m), 3.79 (1H, d), 4.09 (1H,d), 6.43-6.46 (1H, m), 6.58 (1H, d), 7.24-7.26 (2H, m), 7.40-7.40 (1H,m), 7.80 4-12 1H-NMR (acetone-d6) δ: 2.74-2.84 (1H, m), 3.05-3.10 (1H,m), 3.64-3.69 (2H, m), 4.04 (1H, d), 4.40 (1H, d), 6.70-6.77 (2H, m),7.55-7.65 (3H, m), 7.91 (1H, d). 4-13 1H-NMR (CDCl3) δ: 2.53-2.60 (1H,m), 2.84-2.93 (1H, m), 3.52-3.62 (2H, m), 3.80-3.87 (4H, m), 4.11 (1H,d), 6.49-6.52 (1H, m), 6.84 (1H, d), 7.26-7.27 (2H, m), 7.40-7.41 (1H,m), 7.87 (1H, d). 4-14 1H-NMR (CDCl3) δ: 2.51-2.56 (1H, m), 2.85-2.86(1H, m), 3.51-3.57 (2H, m), 3.74-3.87 (4H, m), 4.09 (1H, d), 6.54-6.56(1H, m), 7.17-7.18 (1H, m), 7.27-7.31 (2H, m), 7.38-7.39 (1H, m), 7.854-15 1H-NMR (CDCl3) δ: 2.53-2.60 (4H, m), 2.84-2.85 (1H, m), 3.52-3.62(2H, m), 3.79-3.84 (4H. m), 4.11 (1H, d), 6.39-6.44 (2H, m), 7.26-7.29(2H, m), 7.39-7.39 (1H, m), 7.91-7.94 (1H, m). 4-16 1H-NMR (CDCl3) δ:2.27 (3H, s), 2.49-2.54 (1H, m), 2.78-2.87 (1H, m), 3.38-3.54 (2H, m),3.74 (1H, d, J = 10.4 Hz), 3.99 (1H, d, J = 10.4 Hz), 6.40-6.43 (1H, m),6.60-6.62 (1H, m), 7.05-7.08 4-18 1H-NMR (CDCl3) δ: 2.51-2.64 (1H, m),2.67 (3H, s), 2.87-2.95 (1H, m), 3.51-3.71 (2H, m), 3.84 (1H, d), 4.17(1H, d), 6.37 (1H, d), 6.45 (1H, dd), 7.28 (2H, br s), 7.41 (1H, t),8.14 (1H, d). 4-19 1H-NMR (CDCl3) δ: 2.19 (3H, s), 2.41-2.58 (1H, m),2.73-2.81 (1H, m), 3.15-3.51 (4H, m), 3.73 (1H, d), 3.92 (1H, d),6.34-6.44 (2H, m), 6.66 (1H, d), 7.31-7.41 (3H, m). 4-20 1H-NMR (CDCl3)δ: 2.53-2.66 (1H, m), 2.89-2.97 (1H, m), 3.51-3.71 (2H, m), 3.83 (1H,d), 4.16 (1H, d), 6.53 (1H, dd), 6.84 (1H, d), 7.27 (2H, br s), 7.42(1H, t), 8.07 (1H, d). 4-21 1H-NMR (CDCl3) δ: 2.44-2.54 (1H, m),2.75-2.83 (1H, m), 3.32-3.50 (2H, m), 3.56-3.76 (3H, m), 3.92 (1H, d),6.46 (1H, dd), 6.70-6.78 (2H, m), 7.29 (2H, br s), 7.37 (1H, t). 4-231H-NMR (DMSO-d6) δ: 2.63-2.75 (1H, m), 2.96-3.12 (1H, m), 3.49-3.59 (2H,m), 3.91 (1H, d), 4.41 (1H, d), 6.88 (1H, dd), 7.06 (1H, d), 7.67-7.90(5H, m), 13.00 (1H, br s). 4-24 1H-NMR (CDCl3) δ: 2.61-2.73 (1H, m),3.03-3.13 (1H, m), 3.58-3.75 (2H, m), 3.85 (3H, s), 3.89 (1H, d), 4.29(1H, d), 6.73 (1H, dd), 6.79 (1H, d), 7.80-7.85 (3H, m), 7.95 (1H, brs). 4-25 1H-NMR (DMSO-d6) δ: 2.66-2.80 (1H, m), 3.11-3.22 (1H, m),3.51-3.61 (2H, m), 3.93 (1H, d), 4.51 (1H, d), 6.90 (1H, d), 7.06 (1H,br s), 7.81 (1H, t), 8.22 (3H, br s), 13.03 (1H. br s). 4-26 1H-NMR(CDCl3) δ: 2.54-2.64 (1H, m), 2.89-2.97 (1H, m), 3.50-3.69 (2H, m),3.84(1H, d), 3.85(3H, s), 4.15 (1H, d), 6.68 (1H, dd), 6.74 (1H, d),7.22 (1H, dd), 7.47-7.52 (2H, m), 7.81 (1H, 4-27 1H-NMR (DMSO-d6) δ:2.59-2.74 (1H, m), 2.90-3.00 (1H, m), 3.49-3.57 (2H, m), 3.90 (1H, d),4.30 (1H, d), 6.86 (1H, dd), 7.03 (1H, d), 7.55 (1H, d), 7.73-7.86 (3H,m), 12.98 (1H, br s). 4-29 1H-NMR (DMSO-d6) δ: 2.59-2.71 (1H, m),2.90-3.01 (1H, m), 3.49-3.57 (2H, m), 3.89 (1H, d), 4.31 (1H, d), 6.87(1H, dd), 7.05 (1H, d), 7.50 (3H, br s), 7.64 (1H, br s), 7.78 (1H, d),13.00 (1H, 4-32 1H-NMR (CDCl3) δ: 2.36 (6H, s), 2.56-2.66 (1H, m),2.92-3.00 (1H, m), 3.52-3.69 (2H, m), 3.93- 3.84 (4H, m), 4.17 (1H, d),6.69 (1H, dd), 6.75 (1H, d), 7.14 (2H, s), 7.81 (1H, d). 4-33 1H-NMR(CDCl3) δ: 2.63-2.73 (1H, m), 3.01-3.09 (1H, m), 3.55-3.73 (2H, m), 3.85(3H, s), 3.92 (1H, d), 4.26 (1H, d), 6.71 (1H, dd), 6.77 (1H, d),7.62-7.83 (3H, m), 8.27-8.31 (2H, m). 4-47 1H-NMR (DMSO-d6) δ: 2.66-2.77(1H, m), 3.01-3.10 (1H, m), 3.50-3.62 (2H, m), 3.95 (1H, d), 4.43 (1H,d), 6.89 (1H, d), 7.08 (1H, s), 7.75-7.81 (2H, m), 8.03 (1H, d),8.28-8.35 (2H, m), 13.02 4-48 1H-NMR (DMSO-d6) δ: 2.60-2.72 (1H, m),2.94-3.05 (1H, m), 3.50-3.57 (2H, m), 3.90 (1H, d), 4.32 (1H, d), 6.87(1H, d), 7.03 (1H, s), 7.79 (1H, d, J = 9.0 Hz), 7.88 (2H, s), 13.03(1H, s). 4-49 1H-NMR (CDCl3) δ: 2.64-2.75 (1H, m), 3.18-3.25 (1H, m),3.55-3.63 (2H, m), 3.84 (3H, s), 3.98 (1H, d), 4.50 (1H, d), 6.67-6.74(2H, m), 7.32-7.48 (4H, m), 7.82 (1H, d). 4-50 1H-NMR (DMSO-d6) δ:2.67-2.78 (1H, m), 3.23-3.37 (1H, m), 3.46-3.64 (2H, m), 3.91 (1H, d),4.57 (1H, d), 6.86 (1H, dd), 7.04 (1H, d), 7.43-7.56 (3H, m), 7.64-7.68(1H, m), 7.80 (1H, d), 13.01 4-51 1H-NMR (CDCl3) δ: 2.55-2.65 (1H, m),2.89-2.98 (1H, m), 3.49-3.67 (2H, m), 3.84 (3H, s), 3.86 (1H, d), 4.14(1H, t), 6.66 (1H, dd), 6.73 (1H, d), 7.32 (2H, d), 7.40 (2H, d), 7.80(1H, d). 4-52 1H-NMR (DMSO-d6) δ: 2.58-2.68 (1H, m), 2.88-2.96 (1H, m),3.45-3.60 (2H, m), 3.90 (1H, d), 4.28 (1H, d), 6.85 (1H, dd), 7.03 (1H,d), 7.52 (2H, d), 7.57 (2H, d), 7.78 (1H, d), 13.02 (1H, br s). 4-531H-NMR (CDCl3) δ: 1.37 (3H, t), 2.56-2.61 (1H, m), 2.89-2.94 (1H, m),3.58-3.66 (2H, m), 3.82- 3.85 (1H, m), 4.12-4.16 (1H, m), 4.35 (2H, q),6.67-6.70 (1H, m), 6.88-6.89 (1H, m), 7.25-7.28 4-56 1H-NMR (CDCl3) δ:2.53-2.63 (1H, m), 2.88-2.97 (1H, m), 3.53-3.69 (2H, m), 3.82 (2H, d),3.85 (3H, s), 4.14 (1H, d), 6.69 (1H, dd), 6.75 (1H, d), 7.41 (2H, s),7.81 (1H, d). 4-57 1H-NMR (DMSO-d6) δ: 2.64-2.67 (1H, m), 2.93-3.00 (1H,m), 3.49-3.52 (2H, m), 3.88-3.90 (1H, m), 4.31-4.35 (1H, m), 6.92-6.95(1H, m), 7.18-7.21 (1H, m), 7.67-7.69 (3H, m), 7.89-7.92 (1H, m) 4-581H-NMR (CDCl3) δ: 2.57-2.63 (1H, m), 2.91-2.96 (1H, m), 3.52-3.69 (2H,m), 3.82-3.86 (1H, m), 3.94 (3H, s), 4.11-4.18 (1H, m), 6.73-6.76 (1H,m), 6.89-6.90 (1H, m), 7.27-7.42 (3H, m), 8.01- 4-59 1H-NMR (CDCl3) δ:1.63 (9H, s), 2.53-2.63 (1H, m), 2.87-2.95 (1H, m), 3.53-3.69 (2H, m),3.84 (1H, d), 4.13 (1H, d), 6.86 (1H, dd), 7.28 (2H, d), 7.41 (1H, t),7.95 (1H, d), 8.10 (1H, d). 4-60 1H-NMR (CDCl3) δ: 2.58-2.69 (1H, m),2.93-3.02 (1H, m), 3.63-3.73 (2H, m), 3.93 (1H, d), 4.27 (1H, d), 7.18(1H, d), 7.26 (1H, s), 7.30 (2H, s), 7.41 (1H, s), 8.13 (1H, d), 8.20(1H, s), 9.92 (1H, 4-61 1H-NMR (CDCl3) δ: 1.37 (3H, t), 2.60-2.71 (1H,m), 3.01-3.09 (1H, m), 3.60-3.71 (2H, m), 3.88- 3.90 (1H, m), 4.28-4.36(3H, m), 6.71-6.74 (1H, m), 6.91-6.91 (1H, m), 7.84-7.97 (4H, m) 4-621H-NMR (CDCl3) δ: 2.51-2.61 (1H, m), 2.83-2.91 (1H, m), 3.43-3.58 (2H,m), 3.77 (1H, d), 4.03 (1H, d), 6.71-6.66 (2H, m), 7.10 (1H, t), 7.29(2H, s), 7.39 (1H, s). 4-63 1H-NMR (CDCl3) δ: 2.57-2.68 (1H, m),2.93-3.01 (1H, m), 3.75-3.59 (2H, m), 3.87 (1H, d), 4.20 (1H, d), 6.70(1H, dd), 6.88 (1H, d), 7.28 (2H, d), 7.43 (1H, t), 8.08 (1H, d). 4-651H-NMR (CDCl3) δ: 1.37 (3H, t), 2.53-2.58 (1H, m), 2.85-2.93 (1H, m),3.53-3.62 (2H, m), 3.78- 3.81 (1H, m), 4.08-4.16 (1H, m), 4.34 (2H, q),6.25-6.36 (2H, m), 7.28-7.33 (3H, m), 7.84-7.87 4-66 1H-NMR (CDCl3) δ:1.36 (3H, t), 2.55-2.62 (1H, m), 2.86-2.94 (1H, m), 3.57-3.63 (2H, m),3.80- 3.84 (1H, m), 4.12-4.15 (1H, m), 4.33 (2H, q), 6.67-6.70 (1H, m),6.87-6.88 (1H, m), 7.41-7.45 5-1  1H-NMR (CDCl3) δ: 2.50-2.68 (2H, m),2.74-2.82 (1H, m), 2.90-2.98 (1H, m), 3.16-3.20 (1H, m), 3.61-3.75 (3H,m), 7.20-7.41 (9H, m). 5-2  1H-NMR (CDCl3) δ: 2.45-2.55 (1H, m),2.76-2.85 (1H, m), 3.00-3.09 (1H, m), 3.22-3.35 (2H, m), 4.10 (1H, d),7.23-7.44 (4H, m). 5-3  1H-NMR (CDCl3) δ: 2.33-2.42 (1H, m), 2.55-2.63(1H, m), 2.74-2.78 (2H, m), 3.09 (1H, d), 3.18 (1H, d), 3.67 (2H, s),7.26-7.38 (9H, m). 5-4  1H-NMR (CDCl3) δ: 2.28-2.38 (1H, m), 2.49-2.59(1H, m), 2.97-3.06 (1H, m), 3.19-3.30 (2H, m), 3.75 (1H, d), 7.28-7.33(4H, m). 5-5  1H-NMR (CDCl3) δ: 2.31-2.41 (1H, m), 2.55-2.63 (1H, m),2.70-2.81 (2H, m), 3.08 (1H, d), 3.18 (1H, d), 3.66 (2H, s), 7.24-7.33(9H, m). 5-6  1H-NMR (CDCl3) δ: 2.27-2.36 (1H, m), 2.49-2.59 (1H, m),2.96-3.05 (1H, m), 3.20-3.29 (2H, m), 3.76 (1H, d), 7.28-7.36 (4H, m).5-7  1H-NMR (CDCl3) δ: 2.50-2.66 (2H, m), 2.76-2.84 (1H, m), 2.91-2.99(1H, m), 3.16 (1H, dd), 3.61- 3.75 (3H, m), 7.17 (1H, t), 7.25-7.35 (6H,m), 7.46 (1H, dd). 5-8  1H-NMR (CDCl3) δ: 2.41-2.53 (1H, m), 2.78-2.87(1H, m), 3.00-3.09 (1H, m), 3.23-3.32 (2H, m), 4.11 (1H, d), 7.18-7.30(2H, m), 7.48 (1H, dd). 5-9  1H-NMR (CDCl3) δ: 2.28-2.37 (1H, m),2.54-2.62 (1H, m), 2.70-2.82 (2H, m), 3.06 (1H, d), 3.13 (1H, d), 3.66(2H, s), 7.21-7.33 (6H, m), 7.41 (1H, d), 7.49 (1H, d). 5-10 1H-NMR(CDCl3) δ: 2.25-2.34 (1H, m), 2.50-2.59 (1H, m), 2.97-3.08 (1H, m),3.20-3.28 (2H, m), 3.75 (1H, d), 7.20 (1H, d), 7.44 (2H, d). 5-11 1H-NMR(CDCl3) δ: 2.27-2.36 (1H, m), 2.53-2.62 (1H, m), 2.69-2.83 (2H, m), 3.08(2H, dd), 3.67 5-12 1H-NMR (CDCl3) δ: 2.24-2.33 (1H, m), 2.51-2.56 (1H,m), 2.97-3.07 (1H, m), 3.19-3.26 (2H, m), 3.74 (1H, d), 7.25 (2H, d),7.35 (1H, t). 5-14 1H-NMR (CDCl3) δ: 2.24-2.34 (1H, m), 2.53-2.61 (1H,m), 2.67-2.87 (2H, m), 3.06 (2H, dd), 3.67 (2H, dd), 7.24-7.43 (7H, m).5-15 1H-NMR (CDCl3) δ: 2.22-2.32 (1H, m), 2.49-2.58 (1H, m), 2.98-3.08(1H, m), 3.20-3.29 (2H, m). 5-16 1H-NMR (CDCl3) δ: 2.35-2.44 (1H, m),2.60-2.68 (1H, m), 2.72-2.85 (2H, m), 3.16 (2H, dd), 3.68 (2H, dd),7.28-7.34 (5H, m), 7.46 (1H, t), 7.55-7.60 (2H, m), 7.66 (1H, s). 5-171H-NMR (CDCl3) δ: 2.32-2.41 (1H, m), 2.55-2.65 (1H, m). 2.98-3.07 (1H,m), 3.21-3.33 (2H, m), 3.82 (1H, d), 7.47-7.62 (4H, m). 5-18 1H-NMR(CDCl3) δ: 2.29-2.40 (1H, m), 2.63-2.77 (2H, m), 2.88-2.96 (1H, m), 3.09(1H, d), 3.16 (1H, d), 3.62 (1H, d), 3.76 (1H, d, J = 13.0 Hz),7.28-7.34 (5H, m), 7.83 (1H, s), 7.89 (2H, s). 5-19 1H-NMR (CDCl3) δ:2.30-2.39 (1H, m), 2.61-2.70 (1H, m), 3.02-3.10 (1H, m), 3.24-3.33 (2H,m), 3.86 (1H, d), 7.81 (2H, s). 7.87 (1H, s). 5-24 1H-NMR (CDCl3) δ:2.35-2.44 (1H, m), 2.63-2.90 (3H, m), 3.17 (2H, s), 3.69 (2H, dd),7.26-7.34 (5H, m), 7.53 (1H, t), 7.74 (1H, d), 8.18 (1H, dq), 8.34 (1H,s). 5-25 1H-NMR (CDCl3) δ: 2.34-2.43 (1H, m), 2.59-2.69 (1H, m),3.01-3.10 (1H, m), 3.24-3.35 (2H, m), 3.85 (1H, d), 7.57 (1H, t), 7.72(1H, d), 8.20-8.27 (2H, m). 5-26 1H-NMR (CDCl3) δ: 2.31-2.42 (7H, m),2.55-2.63 (1H, m), 2.75-2.80 (2H, m), 3.11 (2H, dd), 3.67 5-27 1H-NMR(CDCl3) δ: 2.29-2.38 (7H, m), 2.51-2.60 (1H, m), 2.97-3.07 (1H, m),3.21-3.31 (2H, m), 6-1  1H-NMR (CDCl3) δ: 2.34 (6H, s), 5.78-5.80 (1H,m), 6.03-6.04 (1H, m), 7.20 (2H, s). 7-1  1H-NMR (CDCl3) δ: 2.52-2.63(1H, m), 2.88-2.96 (1H, m), 3.60-3.77 (2H, m), 4.00 (1H, d), 4.18- 4.07(2H, m), 4.48 (1H, d), 6.16 (1H, t), 6.43 (1H, d), 7.30 (2H, d), 7.39(1H, t), 7.95 (1H, dd), 8.62 7-2  1H-NMR (CDCl3) δ: 2.52-2.62 (1H, m),2.87-2.96 (1H, m), 3.59-3.75 (2H, m), 4.01 (1H, d), 4.48 (1H, d), 4.75(2H, d), 6.43 (1H, d), 7.25-7.20 (1H, m), 7.31 (2H, d), 7.39 (1H, t),7.47 (1H, s), 7.69 7-3  1H-NMR (CDCl3) δ: 2.49-2.57 (1H, m), 2.60 (3H,s), 2.84-2.92 (1H, m), 3.59-3.70 (2H, m), 3.95- 4.15 (3H, m), 4.45 (1H,d), 5.94 (1H, br s), 6.23 (1H, d), 7.26-7.39 (4H, m), 7.58, (1H, d) 7-7 1H-NMR (CDCl3) δ: 2.54-2.61 (1H, m), 2.89-2.94 (1H, m), 3.65-3.68 (2H,m), 3.94-3.98 (1H, m), 4.10-4.16 (2H, m), 4.45-4.48 (1H, m), 6.37-6.40(1H, m), 7.23-7.38 (4H, m), 8.12-8.15 (1H, m) 7-25 1H-NMR (CDCl3) δ:2.54-2.61 (1H, m), 2.88-2.92 (1H, m), 3.64-3.70 (2H, m), 3.98 (1H, d),4.44 (1H, d), 4.73 (2H, d), 6.54 (1H, d), 7.14-7.40 (6H, m), 7.69-7.74(2H, m), 8.52 (1H, d) 7-26 1H-NMR (CDCl3) δ: 2.53-2.63 (1H, m),2.88-2.96 (1H, m), 3.68-3.71 (2H, m), 4.05-4.16 (3H, m), 4.45 (1H, d),6.03 (1H, br s), 6.55 (1H, d), 7.24-7.37 (4H, m), 7.72 (1H, d) 8-231H-NMR (CDCl3) δ: 2.55-2.65 (1H, m), 2.92-2.97 (1H, m), 3.69-3.77 (2H,m), 3.97-4.01 (1H, m), 4.47-4.51 (1H, m), 4.75 (2H, d), 6.62 (1H, s),7.24-7.36 (6H, m), 7.68-7.70 (1H, m), 8.51-8.52 (2H, 8-24 1H-NMR (CDCl3)δ: 2.58-2.63 (1H, m), 2.93-2.97 (1H, m), 3.71-3.74 (2H, m), 3.96-4.09(3H, m), 4.47-4.51 (1H, m), 6.42-6.44 (1H, m), 6.61 (1H, s), 7.30 (2H,s), 7.40 (1H, s), 8.41 (1H, s) 8-25 1H-NMR (CDCl3) δ: 2.55-2.65 (1H, m),2.91-2.97 (1H, m), 3.68-3.73 (2H, m), 3.97-4.01 (1H, m), 4.48-4.52 (1H,m), 5.74-5.77 (2H, m), 6.62 (1H, s), 7.20-7.37 (3H, m), 8.52 (1H, s)11-47  1H-NMR (CDCl3) δ: 1.37 (3H, t, J = 7.1 Hz), 2.55-2.66 (1H, m),2.91-2.99 (1H, m), 3.73-3.75 (2H, m), 4.00-4.04 (1H, m), 4.36 (2H, q, J= 7.1 Hz), 4.49-4.54 (1H, m), 6.65 (1H, s), 7.30 (2H, s), 7.40 12-4 1H-NMR (CDCl3) δ: 2.52-2.62 (1H, m), 2.87-2.95 (1H, m), 3.61-3.75 (2H,m), 3.88 (3H, s), 4.01 (1H, d), 4.50 (1H, d), 6.39 (1H, d), 7.31 (2H,s), 7.39 (1H, s), 8.06 (1H, dd), 8.84 (1H, d). 12-5  1H-NMR (DMSO-d6) δ:2.61-2.72 (1H, m), 2.90-3.01 (1H, m), 3.57-3.66 (2H, m), 3.96 (1H, d),4.49 (1H, d), 6.67 (1H, d), 7.65 (2H, s), 7.70 (1H, t), 7.97 (1H, dd),8.66 (1H, d), 12.46 (1H, br s). 12-10  1H-NMR (CDCl3) δ: 2.54-2.59 (1H,m), 2.87-2.95 (1H, m), 3.66-3.68 (2H, m), 3.88-3.97 (4H, m), 4.45-4.48(1H, m), 6.30 (1H, d), 7.28-7.30 (2H, m), 7.39 (1H, s), 8.05-8.08 (1H,m)

BIOLOGICAL TEST EXAMPLE 1 Test for larvae of Spodoptera litura

Solvent: 3 parts by weight of dimethylformamide, Emulsifier: 1 part byweight of polyoxyethylene alkyl phenyl ether

To prepare a suitable active compound, 1 part by weight of the activecompound is mixed with the above amount of the solvent containing theabove amount of the emulsifier, and the mixture is diluted with water tothe prescribed concentration.

Leaves of batata are immersed in the sample solution diluted with waterto a prescribed concentration and, after the solution depositing onleaves is air-dried, the resultant leaves are put in a laboratory dishof 9 cm in diameter, into which 10 of third stage larvae of Spodopteralitura are then released, and the dish is then put in a temperaturecontrolled room at 25° C., followed by addition of leaves of batata tothe dish on the second day and fourth day and investigation of thenumber of dead insects after 7 days to calculate the insecticidal ratio.

The results are the averages of two laboratory dishes per group in thistest.

Compounds Nos. 1-3, 1-4, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-14, 1-15,1-16, 1-22, 1-23, 1-25, 1-54, 1-55, 1-56, 1-57, 1-63, 1-73, 1-75, 1-81,1-83, 1-85, 1-86, 1-87, 1-88, 1-90, 1-91, 1-93, 2-8, 2-23, 2-29, 2-40,2-41, 3-3 and 3-4 showed 100% of death rate at a concentration of 100ppm of the active compound.

BIOLOGICAL TEST EXAMPLE 2 Test for Tetranychus urticae (Spraying Test)

To prepare an appropriate formulation of an active compound, 1 part byweight of the active compound is mixed with the aforementioned amount ofthe solvent containing the aforementioned amount of the emulsifier, andthe mixture is diluted to a prescribed concentration with water.

50 to 100 adult mites of Tetranychus urticae are inoculated to leaves ofkidney bean at two-leaf stage planted in a pot of 6 cm in diameter. Oneday after, an ample amount of the diluted aqueous solution of theprescribed concentration of an active compound is sprayed with a spraygun. After the spraying, the pot is kept in a greenhouse for 7 days, andthe acaricidal rate is calculated using the following evaluationciteriae:

Acaricidal rate 100 all mites inoculated are dead 98 1 to 4 mitessurvived/propagated 90 5 to 20 mites survived/propagated 60 Many mitessurvived/propagated, but less than the untreated control, some deadbodies are observed 0 No difference from the untreated control wasobserved

Compounds Nos. 1-3, 1-4, 1-7, 1-8, 1-9, 1-10, 1-12, 1-14, 1-15, 1-16,1-17, 1-20, 1-22, 1-23, 1-25, 1-54, 1-55, 1-56, 1-57, 1-75, 1-81, 1-84,1-86, 1-87, 1-90, 2-29, 3-3 and 3-4 showed an acaricidal rate of morethan 98% at a concentration of 500 ppm of active compound.

BIOLOGICAL TEST EXAMPLE 3 Test for Aulacophora Femoralis (Spraying Test)

Solvent: Dimethylformamide 3 parts by weight

Emulsifier: Polyoxyethylene alkyl phenyl ether 1 part by weight

To prepare an appropriate formulation of an active compound, 1 part byweight of the active compound is mixed with the aforementioned amount ofthe solvent containing the aforementioned amount of the emulsifier, andthe mixture is diluted to a prescribed concentration with water.

Leaves of cucumbers are soaked in a diluted aqueous solution of theprescribed concentration of an active compound prepared in the samemanner as in the aforementioned tests, air-dried, and placed a plasticcup containing sterilized black soil. Into this cup, 5 larvae ofAulacophora femoralis at second instar are then released. After 7 days,the number of dead larvae is counted to calculate the death rate.

Compounds Nos. 1-3, 1-4, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-14, 1-15,1-16, 1-17, 1-18, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-54, 1-55, 1-56,1-57, 1-60, 1-61, 1-80, 1-81, 1-85, 1-87, 1-88, 1-90, 1-91, 2-29, 3-3and 3-4 showed 100% of death rate at a concentration of 100 ppm of theactive compound.

BIOLOGICAL TEST EXAMPLE 4 Test Against Organic Phosphorus Agent- andCarbamate Agent-Resistant Myzus persicas

Solvent: Dimethylformamide 3 parts by weight

Emulsifier: Polyoxyethylene alkyl phenyl ether 1 part by weight

To prepare an appropriate formulation of an active compound, 1 part byweight of the active compound is mixed with the aforementioned amount ofthe solvent containing the aforementioned amount of the emulsifier, andthe mixture is diluted to a prescribed concentration with water.

About 30 to 50 adults of organic phosphorus agent- and carbamateagent-resistant Myzus persicae per seedling are inoculated to leaves ofeggplants at two leaf stage cultured in a pot of 6 cm in diameter. Oneday after the inoculation, an ample amount of the diluted aqueoussolution of the prescribed concentration of an active compound preparedin the same manner as in the aforementioned tests is sprayed with aspray gun. After the spraying, the pot is kept in a greenhouse at 28° C.for 7 days, the death rate is calculated. The test is duplicated.

Compounds Nos. 1-7, 1-10, 1-14 and 1-16 showed 98% of death rate at aconcentration of 500 ppm of the active compound.

BIOLOGICAL TEST EXAMPLE 5 Test for Ctenocephalides felis

Solvent: Dimethylformamide

In order to prepare an appropriate formulation of an active compound, 10mg of the active compound is dissolved in 0.5 mL of the aforementionedsolvent, and the mixture is diluted to a prescribed concentration withblood from domestic animals.

About 10 to 15 adults of Ctenocephalides felis were kept in aflea-specific container. Another container containing the blood solutioncontaining the compound prepared as described above is covered with alaboratory film [PARAFILM (Trademark)]. The blood containing containeris turned upside down and placed on the flea-specific container. Thissystem enables Ctenocephalides felis to suck the blood in the container.The blood solution is kept at 37° C. and the flea-specific container iskept at room temperature. After a certain period of time, the death rateof Ctenocephalides felis is calculated. For this test, the death rate of100% means death of all Ctenocephalides felis, while the death rate of0% means that all the fleas survived.

In this biological test, the compound 1-16 showed more than 80% of deathrate at a concentration of 100 ppm of the active ingredient.

BIOLOGICAL TEST EXAMPLE 6 Test for Boophilus microplus

Solvent: Dimethylformamide

In order to prepare an appropriate formulation of an active compound, 10mg of the active compound is dissolved in 0.5 mL of the aforementionedsolvent, and the mixture is diluted to a prescribed concentration withwater.

A solution of a compound formulated as above is injected into 5 fullyfed adult female Boophilus microplus in their abdomen. These Boophilusmicroplus are transferred to a replica dish and kept in an incubatingcabinet for a certain period of time.

After a certain period of time, the death rate of Boophilus microplus iscalculated. In this test, the death rate of 100% means death of allBoophilus microplus, while the death rate of 0% means that all the mitessurvive.

In the above biological test, the compound 1-16 showed more than 80% ofdeath rate at a dose of 20 g/animal of the active ingredient.

BIOLOGICAL TEST EXAMPLE 7 Test for Lucillia Cuprina

Solvent: Dimethylformamide

In order to prepare an appropriate formulation of an active compound, 10mg of the active compound is dissolved in 0.5 mL of the aforementionedsolvent, and the mixture is diluted to a prescribed concentration withwater.

About 20 to 30 larvae of Lucillia cuprina are placed into a test tubecontaining 1 cm3 of minced horsemeat and 0.5 mL of an aqueous solutionof a compound prepared as above.

After a certain period of time, the death rate of Lucillia cuprina iscalculated. For this test, the death rate of 100% means death of allLucillia cuprina, while the death rate of 0% means that all the fliessurvived.

In this biological test, the compound 1-16 showed more than 80% of deathrate at a concentration of 100 ppm of the active ingredient.

FORMULATION EXAMPLE 1 Granules

To a mixture containing 10 parts of a compound according to theinvention, namely compound No. 1-3, 30 parts of bentonite(montmorillonite), 58 parts of talc and 2 parts of ligninsulfonic acidsalt is added 25 parts of water, and the mixture is well kneaded andgranulated with 10 to 40 meshes by an extruding granulator and dried at40 to 50° C. to obtain granules.

FORMULATION EXAMPLE 2 granules

95 parts of clay mineral granules having particle diameter distributionwithin the range of 0.2 to 2 mm, which is put into a rotary mixer, arewetted evenly by spraying of 5 parts of the compound according to theinvention, namely compound No. 1-3 together with a liquid diluent underrotating condition and dried at 40 to 50° C. to obtain granules.

FORMULATION EXAMPLE 3 Emulsions

30 parts of the compound according to the invention, namely compound No.1-3, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl etherand 7 parts of calcium alkylbenzenesulfonate are mixed together toobtain the emulsion.

FORMULATION EXAMPLE 4 Wettable Agent

15 parts of the compound according to the invention, namely compound No.1-3, 80 parts of a mixture of white carbon (hydrated amorphous siliconoxide fine powder) and powdered clay (1:5), 2 parts of sodiumalkylbenzenesulfonate and 3 parts of sodiumalkylnaphthalenesulfonate-formalin condensate are mixed together and themixture is crushed to obtain water dispersible powder.

FORMULATION EXAMPLE 5 Wettable Granules

20 parts of the active compound according to the invention, namelycompound No. 1-3, 30 parts of sodium ligninsulfonate, 15 parts ofbentonite and 35 parts of calcined diatomaceous earth powder are wellmixed, and after addition of water, which is then extruded with a screenof 0.3 mm and dried to obtain water-dispersible granules.

INDUSTRIAL AVAILABILITY

Novel aryl pyrrolidines of the invention have an excellent insecticidalaction as insecticides as shown in above examples.

1-10. (canceled)
 11. A compound of formula (VIII) or formula (VIII-b):

wherein X which may be same or different, represents halogen, C₁₋₁₂haloalkyl, nitro, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, cyano, C₁₋₁₂ haloalkoxy,C₁₋₁₂ alkylthio, C₁₋₁₂ alkylsulfinyl, C₁₋₁₂ alkylsulfonyl, C₁₋₁₂haloalkylthio, C₁₋₁₂ haloalkylsulfinyl, C₁₋₁₂ haloalkylsulfonyl,hydroxyl, mercapto, amino, C₁₋₁₂ alkylcarbonylamino, C₁₋₁₂haloalkylcarbonylamino, benzoylamino, C₁₋₁₂ alkoxy-carbonylamino, C₁₋₁₂haloalkoxy-carbonylamino, C₁₋₁₂ alkylsulfonylamino or C₁₋₁₂haloalkylsulfonylamino; Y which may be same or different, representshalogen, C₁₋₁₂ haloalkyl, nitro, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, cyano, C₁₋₁₂haloalkoxy, C₁₋₁₂ alkylthio, C₁₋₁₂ alkylsulfinyl, C₁₋₁₂ alkylsulfonyl,C₁₋₁₂ haloalkylthio, C₁₋₁₂ haloalkylsulfinyl, C₁₋₁₂ haloalkylsulfonyl,hydroxyl, mercapto, amino, C₁₋₁₂ alkylcarbonylamino, C₁₋₁₂haloalkylcarbonylamino, benzoylamino, C₁₋₁₂ alkoxy-carbonylamino, C₁₋₁₂haloalkoxy-carbonylamino, C₁₋₁₂ alkylsulfonylamino or C₁₋₁₂haloalkylsulfonylamino; R represents C₁₋₁₂ alkyl or C₁₋₁₂ haloalkyl; R³and R⁴ each independently represents hydrogen, cyano, optionallysubstituted C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₇ cycloalkyl,or C₁₋₁₂ alkoxycarbonyl; or when taken together represent C₂₋₆ alkylene;A represents C or N; l represents 1, 2, or 3; m represents 0, 1,2, 3, 4,or 5; n represents 0, 1, 2, or 4; and L³ represents chlorine, bromine,iodine, C₁₋₄ alkylsulfonyloxy, C₁₋₄ haloalkylsulfonyloxy,arylsulfonyloxy or azolyl.
 12. A compound of formula (X) or formula(X-a):

wherein X which may be same or different, represents halogen, C₁₋₁₂haloalkyl, nitro, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, cyano, C₁₋₁₂ haloalkoxy,C₁₋₁₂ alkylthio, C₁₋₁₂ alkylsulfinyl, C₁₋₁₂ alkylsulfonyl, C₁₋₁₂haloalkylthio, C₁₋₁₂ haloalkylsulfinyl, C₁₋₁₂ haloalkylsulfonyl,hydroxyl, mercapto, amino, C₁₋₁₂ alkylcarbonylamino, C₁₋₁₂haloalkylcarbonylamino, benzoylamino, C₁₋₁₂ alkoxy-carbonylamino, C₁₋₁₂haloalkoxy-carbonylamino, C₁₋₁₂ alkylsulfonylamino or C₁₋₁₂haloalkylsulfonylamino; Y which may be same or different, representshalogen, C₁₋₁₂ haloalkyl, nitro, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, cyano, C₁₋₁₂haloalkoxy, C₁₋₁₂ alkylthio, C₁₋₁₂ alkylsulfinyl, C₁₋₁₂ alkylsulfonyl,C₁₋₁₂ haloalkylthio, C₁₋₁₂ haloalkylsulfinyl, C₁₋₁₂ haloalkylsulfonyl,hydroxyl, mercapto, amino, C₁₋₁₂ alkylcarbonylamino, C₁₋₁₂haloalkylcarbonylamino, benzoylamino, C₁₋₁₂ alkoxy-carbonylamino, C₁₋₁₂haloalkoxy-carbonylamino, C₁₋₁₂ alkylsulfonylamino or C₁₋₁₂haloalkylsulfonylamino; R represents C₁₋₁₂ alkyl or C₁₋₁₂ haloalkyl; R³and R⁴ each independently represents hydrogen, cyano, optionallysubstituted C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₃₋₇ cycloalkyl,or C₁₋₁₂ alkoxycarbonyl; or when taken together represent C₂₋₆ alkylene;R⁵ represents hydrogen, C₁₋₁₂ alkyl, optionally substituted C₃₋₇cycloalkyl, C₁₋₆ haloalkyl, cyano, C₂₋₁₂ alkenyl, C₂₋₁₂ alkynyl, C₁₋₁₂alkylcarbonyl, or CH₂—R⁷; R⁷ represents phenyl or a heterocyclic ring,which are optionally substituted with at least one substituent selectedfrom the group consisting of fluorine, chlorine, bromine, iodine andC₁₋₁₂ alkyl; A represents C or N; l represents 1, 2, or 3; m represents0, 1, 2, 3, 4, or 5; and n represents 0, 1, 2, or
 4. 13. A compound offormula (XXIV) or formula (XXIV-a):

wherein X which may be same or different, represents halogen, C₁₋₁₂haloalkyl, nitro, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, cyano, C₁₋₁₂ haloalkoxy,C₁₋₁₂ alkylthio, C₁₋₁₂ alkylsulfinyl, C₁₋₁₂ alkylsulfonyl, C₁₋₁₂haloalkylthio, C₁₋₁₂ haloalkylsulfinyl, C₁₋₁₂ haloalkylsulfonyl,hydroxyl, mercapto, amino, C₁₋₁₂ alkylcarbonylamino, C₁₋₁₂haloalkylcarbonylamino, benzoylamino, C₁₋₁₂ alkoxy-carbonylamino, C₁₋₁₂haloalkoxy-carbonylamino, C₁₋₁₂ alkylsulfonylamino or C₁₋₁₂haloalkylsulfonylamino; Y which may be same or different, representshalogen, C₁₋₁₂ haloalkyl, nitro, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, cyano, C₁₋₁₂haloalkoxy, C₁₋₁₂ alkylthio, C₁₋₁₂ alkylsulfinyl, C₁₋₁₂ alkylsulfonyl,C₁₋₁₂ haloalkylthio, C₁₋₁₂ haloalkylsulfinyl, C₁₋₁₂ haloalkylsulfonyl,hydroxyl, mercapto, amino, C₁₋₁₂ alkylcarbonylamino, C₁₋₁₂haloalkylcarbonylamino, benzoylamino, C₁₋₁₂ alkoxy-carbonylamino, C₁₋₁₂haloalkoxy-carbonylamino, C₁₋₁₂ alkylsulfonylamino or C₁₋₁₂haloalkylsulfonylamino; R represents C₁₋₁₂ alkyl or C₁₋₁₂ haloalkyl; mrepresents 0, 1, 2, 3, 4, or 5; and n represents 0, 1, 2, or 4.